Generation of peroxyformic acid through polyhydric alcohol formate

ABSTRACT

The present invention relates generally to peroxyformic acid forming compositions, methods for forming peroxyformic acid, preferably in situ, using the peroxyformic acid forming compositions. The present invention also relates to the peroxyformic acid formed by the above compositions and methods. The present invention further relates to the uses of the peroxyformic acid, preferably in situ, for treating a surface or a target. The present invention further relates to methods for treating a biofilm using peroxyformic acid, including peroxyformic acid generated in situ.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority under 35 U.S.C. §119 to provisionalapplication U.S. Ser. No. 62/094,048 filed Dec. 18, 2014, hereinincorporated by reference in its entirety. The entire contents of thispatent application are hereby expressly incorporated herein by referenceincluding, without limitation, the specification, claims, and abstract,as well as any figures, tables, or drawings thereof.

FIELD OF THE INVENTION

The present invention relates generally to peroxyformic acid formingcompositions, methods for forming peroxyformic acid, preferably in situ,using the peroxyformic acid forming compositions. The present inventionalso relates to peroxyformic acid formed by the above compositions andmethods. The present invention further relates to the uses ofperoxyformic acid, preferably in situ, for treating a surface or atarget. The present invention further relates to methods for treating abiofilm using peroxyformic acid, including peroxyformic acid generatedin situ.

BACKGROUND OF THE INVENTION

Among various biocides known, peroxycarboxylic acids are increasinglyused as antimicrobials and bleaching agents in many applications, owingto their high efficacy against a broad spectrum of microorganisms, colorsafe property, low residues and nontoxic nature of their decompositionproducts. Peracetic acid is the most commonly used peroxycarboxylic acidand has been shown to be a good biocide, but only at relatively highconcentrations (generally greater than 80 part per million). Similarly,peroxyfatty acids have also been shown to be biocidal, but only at highconcentrations (greater than 200 ppm), such as in the compositiondisclosed in European Patent Application No. 233,731. In contrast,peroxyformic acid has an advantageous degree and range of microcidalproperties compared to other peroxycarboxylic acids, such as peraceticand perproprionic acids, as disclosed by V. Merka et al in J. Hyg.Epidem. Microbiol. Immunol, 1965 (IX) 220, as well as in European PatentApplication No. 863,098,96.

Peroxycarboxylic acid compositions are generally made through an acidcatalyzed equilibrium reaction. Most often, the peroxycarboxylic acidsare generated in a chemical plant, and then shipped to customers foron-site use. Due to the limited storage stability of peroxycarboxylicacids, the peroxycarboxylic acids must be packed in special containersand shipped under strict Department of Transportation (DOT) guidelines.Further, excess amounts of reagents (e.g., acids, oxidizing agents, andstabilizers) are present in the compositions during shipping to preventdecomposition. For peroxyformic acid, however, the inherent instabilityof the substance relative to the higher alkyl peracid, and the explosivenature of the substance at the concentrate make it an even moresignificant challenge to be manufactured, stored and transported beforedilution prior to use, in the similar way like higher alkyl peracid.Thus, there are needs for the on-site generation of peroxycarboxylicacids, especially peroxyformic acid.

It is known in the art that peroxycarboxylic acids could bealternatively generated in situ through the perhydrolysis of the higheralkyl carboxylic acid esters of polyhydric alcohol, as disclosed in thePatent Application No. WO2012/090124 and U.S. Pat. No. 7,919,122. Theperhydrolysis reaction, however, has to be carried out under strongalkaline conditions, for example at pH greater than 12, or at leastkeeping the pH of the solution between 10 to 12 during the perhydrolysisreaction. As a result, the solution has to be acidified after theperhydrolysis reaction in order to bring the generated peroxycarboxylicacid in the form to be efficient as biocide. One approach to increasethe perhydrolysis reactivity of the esters is using perhydrolysisenzyme, such as disclosed in U.S. Pat. No. 8,865,436. With the help ofthe enzyme, the reaction could be carried out in close to neutral pHconditions, and thus avoid the acid neutralization process. However, theenzyme itself is expensive, and including the enzyme in the system willalso increase the delivery complexity.

There is a need to seek alternative ways to generate peroxycarboxylicacids, namely peroxyformic acids. The present disclosure addresses thisand the related needs using, inter alia, performic acid.

BRIEF SUMMARY OF THE INVENTION

The present invention relates generally to peroxyformic acid formingcompositions, methods for forming peroxyformic acid, preferably in situ,using the peroxyformic acid forming compositions, the peroxyformic acidformed by the above compositions and methods, and the uses of theperoxyformic acid, preferably in situ, for treating a surface or atarget. The present invention further relates to methods for treating abiofilm using peroxyformic acid, including peroxyformic acid generatedin situ.

In one aspect, the present invention is directed to a peroxyformic acidforming composition comprising: a) a first reagent that comprises anester of a polyhydric alcohol and formic acid, and b) a second reagentthat comprises hydrogen peroxide or that comprises a substance thatgenerates hydrogen peroxide when in contact with a liquid, wherein 1)said first reagent and said second reagent are kept separately prior touse, and when it is time to generate peroxyformic acid, said firstreagent and said second reagent are configured to be contacted with eachother to form a liquid that comprises peroxyformic acid and has a pHbelow about 11, and pH of the formed liquid becomes about 8 or lowerwithin about 1 minute after the contact between said first reagent andsaid second reagent; or 2) said second reagent comprises a substancethat generates hydrogen peroxide when in contact with a liquid, saidfirst reagent and said second reagent are comprised in a solidcomposition, and when it is time to generate peroxyformic acid, saidsolid composition is configured to be contacted with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, andpH of the formed liquid becomes about 8 or lower within about 1 minuteafter the contact between said solid composition and said liquid.

In another aspect, the present invention is directed to a method forforming peroxyformic acid comprising: a) contacting a first reagent thatcomprises an ester of a polyhydric alcohol and formic acid, and a secondreagent that comprises hydrogen peroxide or that comprises a substancethat generates hydrogen peroxide when in contact with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11,wherein said first reagent and said second reagent are kept separatelyprior to said contacting and pH of said formed liquid becomes about 8 orlower within about 1 minute after the contact between said first reagentand said second reagent; or b) contacting a solid composition thatcomprises a first reagent that comprises an ester of a polyhydricalcohol and formic acid, and a second reagent that comprises a substancethat generates hydrogen peroxide when in contact with a liquid with aliquid to form a liquid that comprises peroxyformic acid and has a pHbelow about 11, and pH of said formed liquid becomes about 8 or lowerwithin about 1 minute after the contact between said solid compositionand said liquid.

In some embodiments, the use of the above peroxyformic acid formingcompositions and the above methods for forming peroxyformic acid are atleast based on the surprising finding that the formic acid esters ofpolyhydric alcohol, such as glycerol formates, can quickly or instantlygenerate peroxyformic acid in the presence of H₂O₂ under very mild pHconditions in the absence of an enzyme. Furthermore, the pH of thesolution quickly or instantly moved significantly lower after the mixingof the esters and H₂O₂ solution, thus eliminating the need for adjustingpH of the formed liquid.

In another aspect, the present invention is directed to peroxyformicacid formed using the above method.

In still another aspect, the present invention is directed to a methodfor treating a surface or a target, which method comprises a step ofcontacting a surface or a target with an effective amount ofperoxyformic acid formed using the above methods, preferably in situ, toform a treated target composition, wherein said treated targetcomposition comprises from about 0.1 ppm to about 10,000 ppm of saidperoxyformic acid, and said contacting step lasts for sufficient time tostabilize or reduce microbial population in and/or on said surface ortarget or said treated target composition.

In yet another aspect, the present invention is directed to a method fortreating a biofilm, which method comprises contacting a biofilm on asurface with an effective amount of peroxyformic acid for a sufficienttime to stabilize, reduce and/or remove microbial population in and/oron said treated biofilm, or to stabilize, reduce and/or remove saidbiofilm on said surface.

While multiple embodiments are disclosed, still other embodiments of thepresent invention will become apparent to those skilled in the art fromthe following detailed description, which shows and describesillustrative embodiments of the invention. Accordingly, the drawings anddetailed description are to be regarded as illustrative in nature andnot restrictive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates perhydrolysis of various esters according toembodiments of the invention.

FIG. 2 illustrates perhydrolysis of various polyhydric alcohol formicacid esters according to embodiments of the invention.

FIG. 3 illustrates perhydrolysis of glycerol formates under various pHconditions according to embodiments of the invention.

FIG. 4 illustrates generation of peroxyformic acid by repeated additionof glycerol formates according to embodiments of the invention.

FIG. 5 illustrates perhydrolysis of glycerol formate in the presence ofan enzyme according to embodiments of the invention.

FIG. 6A illustrates generation of peroxyformic acid using POAA, glycerolformates and imidazole according to embodiments of the invention.

FIG. 6B illustrates the pH profile of the solution containing the formedperoxyformic acid according to embodiments of the invention.

FIG. 7 illustrates efficacy against C. difficile spores withperoxyformic acid and POAA generated using POAA and glycerol formatesaccording to embodiments of the invention.

FIG. 8 illustrates efficacy against C. difficile spores at various timepoints after the mixing of POAA and glycerol formates according toembodiments of the invention.

FIG. 9A illustrates fast generation of performic acid through theperhydrolysis of glycerol formates according to embodiments of theinvention.

FIG. 9B illustrates the pH profile of the solution containing the formedperoxyformic acid according to embodiments of the invention.

FIG. 10A illustrates generation of performic acid from sugar formatesthrough perhydrolysis according to embodiments of the invention.

FIG. 10B illustrates the pH profile of the solution containing theformed peroxyformic acid according to embodiments of the invention.

FIG. 11 illustrates reduction of P. aeruginosa biofilm using differentconcentrations of peroxyformic acid compared to peroxyacetic acidcompositions according to embodiments of the invention.

FIG. 12 illustrates reduction of P. aeruginosa biofilm using differentexposure times of peroxyformic acid according to embodiments of theinvention.

FIG. 13 illustrates the perhydrolysis kinetics of the glycerol premixstored for different periods demonstrating stability according toembodiments of the invention.

FIG. 14 illustrates peroxyformic acid generation through perhydrolysisof glycerol formate premixes according to embodiments of the invention.

FIG. 15 illustrates the pH impact on peroxyformic acid generationthrough perhydrolysis of glycerol formate premixes according toembodiments of the invention.

FIG. 16 illustrates improved micro efficacy (log reduction) achievedfrom peroxyformic acid compositions in comparison to peroxyacetic acidaccording to embodiments of the invention.

FIG. 17 illustrates improved micro efficacy (log reduction) achievedfrom peroxyformic acid compositions in comparison to peroxyacetic acidaccording to embodiments of the invention.

FIG. 18 illustrates equivalent micro efficacy (log reduction) achievedfor spores from peroxyformic acid compositions in comparison toperoxyacetic acid (when dosed at lower actives) according to embodimentsof the invention.

FIG. 19 illustrates improved micro efficacy (log reduction) achieved forspores from peroxyformic acid compositions in comparison to peroxyaceticacid according to embodiments of the invention.

FIG. 20 illustrates micro efficacy of peroxyformic acid compositions incomparison to peroxyacetic acid according to embodiments of theinvention.

FIG. 21 illustrates the bleaching efficacy of performic acid generatedaccording to embodiments of the invention.

FIG. 22 illustrates the stability of peroxyformic acid in high soilloads according to embodiments of the invention.

FIG. 23 shows the generation of peroxyformic acid using a concentrateglycerol formate and acid peroxide premix according to embodiments ofthe invention.

FIG. 24 shows the impact of the ratio of the glycerol formate and acidperoxide premix for maximizing peroxyformic acid yield according toembodiments of the invention.

FIG. 25 shows the peroxyformic acid generation with the acid premixconcentrate according to embodiments of the invention.

Various embodiments of the present invention will be described in detailwith reference to the drawings, wherein like reference numeralsrepresent like parts throughout the several views. Reference to variousembodiments does not limit the scope of the invention. Figuresrepresented herein are not limitations to the various embodimentsaccording to the invention and are presented for exemplary illustrationof the invention.

DETAILED DESCRIPTION OF THE INVENTION

The embodiments of this invention are not limited to particularperoxyformic acid forming compositions, methods for forming peroxyformicacid, the formed peroxyformic acid and methods for using the same, whichcan vary and are understood by skilled artisans. It is further to beunderstood that all terminology used herein is for the purpose ofdescribing particular embodiments only, and is not intended to belimiting in any manner or scope. For example, all units, prefixes, andsymbols may be denoted in its SI accepted form. Numeric ranges recitedwithin the specification are inclusive of the numbers defining the rangeand include each integer within the defined range.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as is commonly understood by one of ordinary skillin the art to which this invention belongs. All patents, applications,published applications and other publications referred to herein areincorporated by reference in their entireties. If a definition set forthin this section is contrary to or otherwise inconsistent with adefinition set forth in the patents, applications, publishedapplications and other publications that are herein incorporated byreference, the definition set forth in this section prevails over thedefinition that is incorporated herein by reference. So that the presentinvention may be more readily understood, certain terms are firstdefined. Unless defined otherwise, all technical and scientific termsused herein have the same meaning as commonly understood by one ofordinary skill in the art to which embodiments of the invention pertain.Many methods and materials similar, modified, or equivalent to thosedescribed herein can be used in the practice of the embodiments of thepresent invention without undue experimentation, the preferred materialsand methods are described herein. In describing and claiming theembodiments of the present invention, the following terminology will beused in accordance with the definitions set out below.

It should be noted that, as used in this specification and the appendedclaims, the singular forms “a,” “an,” and “the” include plural referentsunless the content clearly dictates otherwise. Thus, for example,reference to a composition containing “a compound” includes acomposition having two or more compounds. It should also be noted thatthe term “or” is generally employed in its sense including “and/or”unless the content clearly dictates otherwise.

As used herein, the term “about” refers to variation in the numericalquantity that can occur, for example, through typical measuring andliquid handling procedures used for making concentrates or use solutionsin the real world; through inadvertent error in these procedures;through differences in the manufacture, source, or purity of theingredients used to make the compositions or carry out the methods; andthe like. The term “about” also encompasses amounts that differ due todifferent equilibrium conditions for a composition resulting from aparticular initial mixture. Whether or not modified by the term “about”,the claims include equivalents to the quantities.

The term “actives” or “percent actives” or “percent by weight actives”or “actives concentration” are used interchangeably herein and refers tothe concentration of those ingredients involved in cleaning expressed asa percentage minus inert ingredients such as water or salts.

The term “cleaning,” as used herein, means to perform or aid in soilremoval, bleaching, microbial population reduction, or combinationthereof. For the purpose of this patent application, successfulmicrobial reduction is achieved when the microbial populations arereduced by at least about 50%, or by significantly more than is achievedby a wash with water. Larger reductions in microbial population providegreater levels of protection.

As used herein, “consisting essentially of” means that the methods andcompositions may include additional steps, components, ingredients orthe like, but only if the additional steps, components and/oringredients do not materially alter the basic and novel characteristicsof the claimed methods and compositions.

As used herein, the term “disinfectant” refers to an agent that killsall vegetative cells including most recognized pathogenicmicroorganisms, using the procedure described in A.O.A.C. Use DilutionMethods, Official Methods of Analysis of the Association of OfficialAnalytical Chemists, paragraph 955.14 and applicable sections, 15thEdition, 1990 (EPA Guideline 91-2). As used herein, the term “high leveldisinfection” or “high level disinfectant” refers to a compound orcomposition that kills substantially all organisms, except high levelsof bacterial spores, and is effected with a chemical germicide clearedfor marketing as a sterilant by the Food and Drug Administration. Asused herein, the term “intermediate-level disinfection” or “intermediatelevel disinfectant” refers to a compound or composition that killsmycobacteria, most viruses, and bacteria with a chemical germicideregistered as a tuberculocide by the Environmental Protection Agency(EPA). As used herein, the term “low-level disinfection” or “low leveldisinfectant” refers to a compound or composition that kills someviruses and bacteria with a chemical germicide registered as a hospitaldisinfectant by the EPA.

As used herein, the phrase “food processing surface” refers to a surfaceof a tool, a machine, equipment, a structure, a building, or the likethat is employed as part of a food or beverage processing, preparation,or storage activity. Food processing surface is intended to encompassall surfaces used in brewing (including beer brewing and preparation ofliquors and spirits) and winemaking processes (e.g., bright beer tanksand lines, fermentation vessels, mash tuns, bottling equipment, pipes,and storage vessels). Examples of food processing surfaces includesurfaces of food processing or preparation equipment (e.g., boiling,fermenting, slicing, canning, or transport equipment, including flumes),of food processing wares (e.g., utensils, dishware, wash ware, and barglasses), and of floors, walls, or fixtures of structures in which foodprocessing occurs. Food processing surfaces are found and employed infood anti-spoilage air circulation systems, aseptic packagingsanitizing, food refrigeration and cooler cleaners and sanitizers, warewashing sanitizing, blancher cleaning and sanitizing, food packagingmaterials, cutting board additives, third-sink sanitizing, beveragechillers and warmers, meat chilling or scalding waters, autodishsanitizers, sanitizing gels, cooling towers, food processingantimicrobial garment sprays, and non-to-low-aqueous food preparationlubricants, oils, and rinse additives.

As used herein, the phrase “food product” includes any food substancethat might require treatment with an antimicrobial agent or compositionand that is edible with or without further preparation. Food productsinclude meat (e.g. red meat and pork), seafood, poultry, produce (e.g.,fruits and vegetables), eggs, living eggs, egg products, ready to eatfood, wheat, seeds, roots, tubers, leafs, stems, corns, flowers,sprouts, seasonings, or a combination thereof. The term “produce” refersto food products such as fruits and vegetables and plants orplant-derived materials that are typically sold uncooked and, often,unpackaged, and that can sometimes be eaten raw.

As used herein, the term “free,” “no,” “substantially no” or“substantially free” refers to a composition, mixture, or ingredientthat does not contain a particular compound or to which a particularcompound or a particular compound-containing compound has not beenadded. In some embodiments, the reduction and/or elimination of hydrogenperoxide according to embodiments provide hydrogen peroxide-free orsubstantially-free compositions. Should the particular compound bepresent through contamination and/or use in a minimal amount of acomposition, mixture, or ingredients, the amount of the compound shallbe less than about 3 wt-%. More preferably, the amount of the compoundis less than 2 wt-%, less than 1 wt-%, and most preferably the amount ofthe compound is less than 0.5 wt-%.

The term “hard surface” refers to a solid, substantially non-flexiblesurface such as a counter top, tile, floor, wall, panel, window,plumbing fixture, kitchen and bathroom furniture, appliance, engine,circuit board, and dish. Hard surfaces may include for example, healthcare surfaces and food processing surfaces.

As used herein, the phrase “health care surface” refers to a surface ofan instrument, a device, a cart, a cage, furniture, a structure, abuilding, or the like that is employed as part of a health careactivity. Examples of health care surfaces include surfaces of medicalor dental instruments, of medical or dental devices, of electronicapparatus employed for monitoring patient health, and of floors, walls,or fixtures of structures in which health care occurs. Health caresurfaces are found in hospital, surgical, infirmity, birthing, mortuary,and clinical diagnosis rooms. These surfaces can be those typified as“hard surfaces” (such as walls, floors, bed-pans, etc.,), or fabricsurfaces, e.g., knit, woven, and non-woven surfaces (such as surgicalgarments, draperies, bed linens, bandages, etc.,), or patient-careequipment (such as respirators, diagnostic equipment, shunts, bodyscopes, wheel chairs, beds, etc.,), or surgical and diagnosticequipment. Health care surfaces include articles and surfaces employedin animal health care.

As used herein, the term “instrument” refers to the various medical ordental instruments or devices that can benefit from cleaning with acomposition according to the present invention. As used herein, thephrases “medical instrument,” “dental instrument,” “medical device,”“dental device,” “medical equipment,” or “dental equipment” refer toinstruments, devices, tools, appliances, apparatus, and equipment usedin medicine or dentistry. Such instruments, devices, and equipment canbe cold sterilized, soaked or washed and then heat sterilized, orotherwise benefit from cleaning in a composition of the presentinvention. These various instruments, devices and equipment include, butare not limited to: diagnostic instruments, trays, pans, holders, racks,forceps, scissors, shears, saws (e.g. bone saws and their blades),hemostats, knives, chisels, rongeurs, files, nippers, drills, drillbits, rasps, burrs, spreaders, breakers, elevators, clamps, needleholders, carriers, clips, hooks, gouges, curettes, retractors,straightener, punches, extractors, scoops, keratomes, spatulas,expressors, trocars, dilators, cages, glassware, tubing, catheters,cannulas, plugs, stents, scopes (e.g., endoscopes, stethoscopes, andarthoscopes) and related equipment, and the like, or combinationsthereof.

As used herein, the term “laundry” refers to items or articles that arecleaned in a laundry washing machine. In general, laundry refers to anyitem or article made from or including textile materials, woven fabrics,non-woven fabrics, and knitted fabrics. The textile materials caninclude natural or synthetic fibers such as silk fibers, linen fibers,cotton fibers, polyester fibers, polyamide fibers such as nylon, acrylicfibers, acetate fibers, and blends thereof including cotton andpolyester blends. The fibers can be treated or untreated. Exemplarytreated fibers include those treated for flame retardancy. It should beunderstood that the term “linen” is often used to describe certain typesof laundry items including bed sheets, pillow cases, towels, tablelinen, table cloth, bar mops and uniforms.

As used herein, the term “microorganism” refers to any noncellular orunicellular (including colonial) organism. Microorganisms include allprokaryotes. Microorganisms include bacteria (including cyanobacteria),spores, lichens, fungi, protozoa, virinos, viroids, viruses, phages, andsome algae. As used herein, the term “microbe” is synonymous withmicroorganism.

As used herein, the terms “mixed” or “mixture” when used relating to“percarboxylic acid composition,” “percarboxylic acids,”“peroxycarboxylic acid composition” or “peroxycarboxylic acids” refer toa composition or mixture including more than one percarboxylic acid orperoxycarboxylic acid.

As used herein, the term “sanitizer” refers to an agent that reduces thenumber of bacterial contaminants to safe levels as judged by publichealth requirements. In an embodiment, sanitizers for use in thisinvention will provide at least a 99.999% reduction (5-log orderreduction). These reductions can be evaluated using a procedure set outin Germicidal and Detergent Sanitizing Action of Disinfectants, OfficialMethods of Analysis of the Association of Official Analytical Chemists,paragraph 960.09 and applicable sections, 15th Edition, 1990 (EPAGuideline 91-2). According to this reference a sanitizer should providea 99.999% reduction (5-log order reduction) within 30 seconds at roomtemperature, 25±2° C., against several test organisms.

Differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are considerations forunderstanding the relevance of antimicrobial agents and compositions.Antimicrobial compositions can affect two kinds of microbial celldamage. The first is a lethal, irreversible action resulting in completemicrobial cell destruction or incapacitation. The second type of celldamage is reversible, such that if the organism is rendered free of theagent, it can again multiply. The former is termed microbiocidal and thelater, microbistatic. A sanitizer and a disinfectant are, by definition,agents which provide antimicrobial or microbiocidal activity. Incontrast, a preservative is generally described as an inhibitor ormicrobistatic composition.

As used herein, the term “water” for treatment according to theinvention includes a variety of sources, such as freshwater, pond water,sea water, salt water or brine source, brackish water, recycled water,or the like. Waters are also understood to optionally include both freshand recycled water sources (e.g. “produced waters”), as well as anycombination of waters for treatment according to the invention. In someembodiments, produced water (or reuse water) refers to a mixture ofwater that comprises both water recycled from previous or concurrentoil- and gas-field operations, e.g., fracking, and water that has notbeen used in oil- and gas-field operations, e.g., fresh water, pondwater, sea water, etc.

As used herein, “weight percent,” “wt-%,” “percent by weight,” “% byweight,” and variations thereof refer to the concentration of asubstance as the weight of that substance divided by the total weight ofthe composition and multiplied by 100. It is understood that, as usedhere, “percent,” “%,” and the like are intended to be synonymous with“weight percent,” “wt-%,” etc.

It is understood that aspects and embodiments of the invention describedherein include “consisting” and/or “consisting essentially of” aspectsand embodiments.

Throughout this disclosure, various aspects of this invention arepresented in a range format. It should be understood that thedescription in range format is merely for convenience and brevity andshould not be construed as an inflexible limitation on the scope of theinvention. Accordingly, the description of a range should be consideredto have specifically disclosed all the possible sub-ranges as well asindividual numerical values within that range. For example, descriptionof a range such as from 1 to 6 should be considered to have specificallydisclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numberswithin that range, for example, 1, 2, 3, 4, 5, and 6. This appliesregardless of the breadth of the range.

Other objects, advantages and features of the present invention willbecome apparent from the following specification taken in conjunctionwith the accompanying drawings.

Peroxyformic Acid Forming Compositions

The present invention relates to peroxyformic acid forming compositionsand uses thereof. In one aspect, the present invention is directed to aperoxyformic acid forming composition comprising: a) a first reagentthat comprises an ester of a polyhydric alcohol and formic acid, and b)a second reagent that comprises hydrogen peroxide or that comprises asubstance that generates hydrogen peroxide when in contact with aliquid, wherein 1) said first reagent and said second reagent are keptseparately prior to use, and when it is time to generate peroxyformicacid, said first reagent and said second reagent are configured to becontacted with each other to form a liquid that comprises peroxyformicacid and has a pH below about 11, and pH of the formed liquid becomesabout 8 or lower within about 1 minute after the contact between saidfirst reagent and said second reagent; or 2) said second reagentcomprises a substance that generates hydrogen peroxide when in contactwith a liquid, said first reagent and said second reagent are comprisedin a solid composition, and when it is time to generate peroxyformicacid, said solid composition is configured to be contacted with a liquidto form a liquid that comprises peroxyformic acid and has a pH belowabout 11, and pH of the formed liquid becomes about 8 or lower withinabout 1 minute after the contact between said solid composition and saidliquid.

In some embodiments, the present peroxyformic acid forming compositioncomprises a) a first reagent that comprises an ester of a polyhydricalcohol and formic acid, and b) a second reagent that comprises hydrogenperoxide or that comprises a substance that generates hydrogen peroxidewhen in contact with a liquid, wherein said first reagent and saidsecond reagent are kept separately prior to use, and when it is time togenerate peroxyformic acid, said first reagent and said second reagentare configured to be contacted with each other to form a liquid thatcomprises peroxyformic acid and has a pH below about 11, and pH of theformed liquid becomes about 8 or lower within about 1 minute after thecontact between said first reagent and said second reagent. In otherembodiments, the present peroxyformic acid forming composition comprisesa) a first reagent that comprises an ester of a polyhydric alcohol andformic acid, and b) a second reagent that comprises a substance thatgenerates hydrogen peroxide when in contact with a liquid, wherein saidfirst reagent and said second reagent are comprised in a solidcomposition, and when it is time to generate peroxyformic acid, saidsolid composition is configured to be contacted with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, andpH of the formed liquid becomes about 8 or lower within about 1 minuteafter the contact between said solid composition and said liquid.

The present peroxyformic acid forming compositions can comprise anysuitable ester of a polyhydric alcohol and formic acid. Typically, apolyhydric alcohol refers to a molecule with two or more hydroxyl (—OH)groups. An ester of a polyhydric alcohol and formic acid refers to anester formed between a polyhydric alcohol and formic acid. Esters asreferred to herein are considered ‘water-less’ systems as no additionalwater is added to the reaction. In some embodiments, the presentperoxyformic acid forming compositions comprise glycerol formates,pentaerythritol formates, mannitol formates, propylene glycol formates,sorbitol formates and sugar formates. The present peroxyformic acidforming compositions can comprise any suitable sugar formates, e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates.

In a preferred embodiment, a liquid reaction employs glycerol formates,pentaerythritol formates, mannitol formates, or propylene glycolformates. In a still further preferred embodiment, a liquid reactionemploys glycerol formates. Beneficially, the glycerol formates rapidlyundergo hydrolysis for peroxyformic acid generation according to themethods of the invention. In an aspect, the precursors provided do notinclude additional water added into the system which would negativelyinterfere with the kinetics of the reaction between the ester of apolyhydric alcohol and formic acid and hydrogen peroxide. In an aspect,the premixes and the peroxyformic acid forming composition do not addfree water into the systems, which would negatively interfere with theester, e.g. glycerol formates.

In a preferred embodiment, a solid reaction employs sugar formates e.g.,sucrose formates, dextrin formates, maltodextrin formates, or starchformates. In a still further preferred embodiment, a solid reactionemploys starch formates.

The present peroxyformic acid forming compositions can comprise a usesolution or a concentrate of the ester of a polyhydric alcohol andformic acid. In some aspects, the methods of the invention generate aperoxyformic acid through a concentrate reaction of the ester of apolyhydric alcohol and formic acid. In other aspects, the methods of theinvention generate a peroxyformic acid through a diluted use solutionreaction of the ester of a polyhydric alcohol and formic acid.

The first or second reagent can have any suitable pH range in thepresent peroxyformic acid forming compositions. For example, the firstor second reagent can have a pH below about 11, or from about −2 toabout 11, or from about 0 to about 11, e.g., about −2 to about −1, −2 toabout 0, 0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2,1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7,2-8, 2-9, 2-10, 2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5,4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7,6-8, 6-9, 6-10, 6-11, 6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10,9-11, 10-11, or at about −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.In some embodiments, the first or second reagent has a pH ranging fromabout 5 to about 10, e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8,6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, or 9-10. In other embodiments, thefirst or second reagent has a pH at about 9.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid and has any suitable pH, including a pHbelow about 11, or from about −2 to about 11, or from about 0 to about11, e.g., about −2 to about −1, −2 to about 0, 0-1, 0-2, 0-3, 0-4, 0-5,0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9,1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5,3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11,5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11, 6-7, 7-8,7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or at about −2, −1,0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the firstreagent and the second reagent are configured to be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid and has a pH ranging from about −2 to about 11, 0 to about 10, or 5to about 10, e.g., about −2-0, 0-1, 1-2, 2-3, 3-4, 4-5, 5-6, 5-7, 5-8,5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9, 7-10, 8-9, 8-10, 9-10, or10-11. In other embodiments, the first reagent and the second reagentare configured to be contacted with each other to form a liquid, e.g., asolution, that comprises peroxyformic acid and has a pH at about 9. In apreferred aspect, the formed liquid, e.g., a solution, that comprisesperoxyformic acid and has a pH near neutral, from about 6-7.

The pH of the formed liquid can become about 8 or lower within about 1minute after the contact between the first reagent and the secondreagent or after the contact between the solid composition and theliquid. In some embodiments, the pH of the formed liquid can becomeabout 8 or lower within about 1 second, 2 seconds, 3 seconds, 4 seconds,5 seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds after the contact betweenthe first reagent and the second reagent or after the contact betweenthe solid composition and the liquid. In other embodiments, the pH ofthe formed liquid comprising peroxyformic acid becomes about 8 or lowerwithin about 1 minute or less. In an aspect, the pH of the formed liquidcomprising peroxyformic acid becomes about 8 or lower within about 45seconds or less, 40 seconds or less, 35 seconds or less, 30 seconds orless, 25 seconds or less, 20 seconds or less, 15 seconds or less, 10seconds or less, or 5 seconds or less. In an aspect, the pH of theformed liquid comprising peroxyformic acid becomes about 8 or lower nearinstantaneously. In other embodiments, the pH of the formed liquid canbecome about lower than −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, or 8 withinabout 1 minute after the contact between the first reagent and thesecond reagent or after the contact between the solid composition andthe liquid.

The liquid that comprises peroxyformic acid can maintain the pH rangingfrom about −2 to about 8, or from about 0 to about 8 for any suitabletime after the contact between the first reagent and the second reagent,or after the contact between the composition and a liquid. In someembodiments, the liquid that comprises peroxyformic acid maintains thepH ranging from about −2 to about 8, or from about 0 to about 8 fromabout 1 second to about 10 hours after the contact between the firstreagent and the second reagent or after the contact between thecomposition and a liquid. For example, the liquid that comprisesperoxyformic acid can maintain the pH at about −2, −1, 0, 1, 2, 3, 4, 5,6, 7, or 8 from about 1 second to about 10 hours after the contactbetween the first reagent and the second reagent or after the contactbetween the composition and a liquid. In another example, the liquidthat comprises peroxyformic acid can maintain the pH ranging from about0 to about 8 for about 1 second, 2 seconds, 3 seconds, 4 seconds, 5seconds, 6 seconds, 7 seconds, 8 seconds, 9 seconds, 10 seconds, 20seconds, 30 seconds, 40 seconds, 50 seconds, 1 minute, 2 minutes, 3minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9hours, or 10 hours. In a preferred aspect, the formed liquid, e.g., asolution, that comprises peroxyformic acid and has a pH near neutral,from about 6-7 in a use solution.

In some embodiments, the first reagent and the second reagent areconfigured to be contacted with each other to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 4 to about 8or 9, e.g., about 4-5, 5-6, 6-7, 7-8, or 8-9. In a preferred aspect, theformed liquid, e.g., a solution, that comprises peroxyformic acid andhas a pH near neutral, from about 6-7 in a use solution. In one example,the first reagent and the second reagent are configured to be contactedwith each other to form a solution that comprises peroxyformic acid andhas a pH ranging from about 6 to about 8 or 9. The first reagent and thesecond reagent can be configured to be contacted with each other to forma solution that comprises peroxyformic acid and has a pH ranging fromabout 4 to about 8 or 9, and the solution can maintain the pH range forany suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours.

In other embodiments, the solid composition is configured to becontacted with a liquid to form a solution that comprises peroxyformicacid and has a pH ranging from about 4 to about 8 or 9, e.g., about 4-5,5-6, 6-7, 7-8, or 8-9. In one example, the solid composition isconfigured to be contacted with a liquid to form a solution thatcomprises peroxyformic acid and has a pH ranging from about 6 to about 8or 9. The solid composition is configured to be contacted with a liquidto form a solution that comprises peroxyformic acid and has a pH rangingfrom about 4 to about 8 or 9, and the solution can maintain the pH rangefor any suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours. In a preferred aspect, the formed liquid, e.g., a solution,that comprises peroxyformic acid and has a pH near neutral, from about6-7 in a use solution.

The first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid under any suitable conditions ortemperature. In some embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises peroxyformic acid at a temperatureranging from about −2° C. to about 60° C., 0° C. to about 60° C., or 4°C. to about 60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C.,4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C.,25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50°C., 50° C.-55° C., or 55° C.-60° C. In still other embodiments, thefirst reagent and the second reagent are configured to be contacted witheach other to form a liquid, e.g., a solution, that comprisesperoxyformic acid at a temperature at about 4° C. or lower than 4° C.,e.g., at about 3° C., 2° C., 1° C., 0° C., or lower than 0° C.

The solid composition can be configured to be contacted with a liquid toform a liquid, e.g., a solution, that comprises peroxyformic acid underany suitable conditions or temperature. In some embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid under ambientconditions. In other embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises peroxyformic acid at a temperature ranging fromabout −2° C. to about 60° C., 0° C. to about 60° C., or 4° C. to about60° C., e.g., about −2° C.-0° C., 0° C.-4° C., 4° C.-5° C., 4° C.-5° C.,5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25° C.-30°C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C., 50°C.-55° C., or 55° C.-60° C. In still other embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises peroxyformic acid at atemperature at about 4° C. or lower than 4° C., e.g., at about 3° C., 2°C., 1° C., 0° C., or lower than 0° C.

The present peroxyformic acid forming compositions can further comprisea catalyst (e.g. mineral acid) or an enzyme that catalyzes formation ofperoxyformic acid from the ester of a polyhydric alcohol and formicacid, and hydrogen peroxide. The present peroxyformic acid formingcompositions can comprise any suitable catalyst, e.g., a strong mineralacid, or enzyme, e.g., a perhydrolytic enzyme, lipase, coronase,termanyl or esperease. The catalyst or an enzyme can be comprised in anysuitable part of the present peroxyformic acid forming compositions. Insome embodiments, the first reagent comprises the catalyst or enzyme. Inother embodiments, the second reagent comprises the catalyst or enzyme.In still other embodiments, the present peroxyformic acid formingcompositions can further comprise a third reagent that comprises thecatalyst or enzyme. In yet other embodiments, the solid compositioncomprises the catalyst or enzyme.

The present peroxyformic acid forming compositions can further comprisea stabilizing agent for peroxyformic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent. In an aspect thestabilizing agent(s) and/or pH buffering agents are useful in decreasinga pH of the compositions to neutral or lower pH. The presentperoxyformic acid forming compositions can comprise any suitablestabilizing agent. Exemplary stabilizing agents include a phosphonatesalt(s) and/or a heterocyclic dicarboxylic acid, e.g., dipicolinic acid.In some embodiments, the stabilizing agent is pyridine carboxylic acidbased stabilizers, such as picolinic acid and salts,pyridine-2,6-dicarboxylic acid and salts, and phosphonate basedstabilizers, such as phosphoric acid and salts, pyrophosphoric acid andsalts and most commonly 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)and salts. In other embodiments, the present peroxyformic acid formingcompositions comprise two or more stabilizing agents, e.g., HEDP and2,6-pyridinedicarboxylic acid (DPA).

The stabilizing agent(s) can be comprised in any suitable part of thepresent peroxyformic acid forming compositions. In some embodiments, thefirst reagent comprises a stabilizing agent for peroxyformic acid and/ora pH buffering agent. In other embodiments, the second reagent comprisesa stabilizing agent for hydrogen peroxide. In still other embodiments,the present peroxyformic acid forming compositions can further comprisea third reagent that comprises a stabilizing agent for peroxyformicacid, a stabilizing agent for hydrogen peroxide, and/or a pH bufferingagent. In yet other embodiments, the solid composition comprises astabilizing agent for peroxyformic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent.

The present peroxyformic acid forming compositions can comprise anysuitable pH buffering agent. The pH buffer reagent can include anyreagent that is compatible with the ester(s) in the present peroxyformicacid forming compositions. Exemplary buffer agents suitable for usingwith a liquid ester can be an organic amine, such as triethanol amine,imidazole, etc. Exemplary buffer agents suitable for using with a solidform of ester include a broader range of buffers, such as a carbonatesalt, a phosphate salt, etc. The pH buffer reagent can be comprised inany suitable part of the present peroxyformic acid forming compositions.In some embodiments, the first reagent comprises a pH buffering agent.In other embodiments, the present peroxyformic acid forming compositionscan further comprise a third reagent that comprises a pH bufferingagent. In still other embodiments, the solid composition comprises a pHbuffering agent.

The present peroxyformic acid forming compositions can comprise anysuitable stabilizing agent for hydrogen peroxide. Exemplary stabilizingagents for hydrogen peroxide include phosphonates, heterocycliccarboxylic acids and the mixtures thereof. In some embodiments,stabilizing agents for hydrogen peroxide can be Dequest 2010, Dequest2066, Dipicolinic acids, etc. The stabilizing agent for hydrogenperoxide can be comprised in any suitable part of the presentperoxyformic acid forming compositions. In some embodiments, the secondreagent comprises a stabilizing agent for hydrogen peroxide. In otherembodiments, the present peroxyformic acid forming compositions canfurther comprise a third reagent that comprises a stabilizing agent forhydrogen peroxide. In still other embodiments, the solid compositioncomprises a stabilizing agent for hydrogen peroxide.

The present peroxyformic acid forming compositions can comprise anysuitable number of dosage(s) of the first reagent that is keptseparately prior to use, and is used to contact the second reagent thatcomprises hydrogen peroxide. For example, the present peroxyformic acidforming compositions can comprise a single dosage of the first reagentthat is kept separately prior to use, and is used to contact the secondreagent that comprises hydrogen peroxide. In another example, thepresent peroxyformic acid forming compositions can comprise multipledosages of the first reagent that are kept separately prior to use, andare used to contact the second reagent that comprises hydrogen peroxide,either simultaneously or sequentially. The multiple dosages of the firstreagent can comprise any suitable ester(s) of a polyhydric alcohol andformic acid. For example, the multiple dosages of the first reagent cancomprise the same ester of a polyhydric alcohol and formic acid. Inanother example, the multiple dosages of the first reagent can comprisedifferent esters of polyhydric alcohols and formic acid. The multipledosages of the first reagent can comprise the same or differentconcentrations of ester(s) of a polyhydric alcohol and formic acid. Instill another example, the present peroxyformic acid formingcompositions can comprise multiple dosages of the solid composition thatare kept separately prior to use.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of an ester of a polyhydric alcohol and formicacid. For example, the first reagent of the peroxyformic acid formingcomposition can comprise any suitable concentration of an ester of apolyhydric alcohol and formic acid. In some embodiments, the formedliquid is a concentrate and comprises the first reagent in an amount upto about 90% of an ester of a polyhydric alcohol and formic acid. Inother embodiments, the formed liquid comprises the first reagent in anamount from about 1 ppm to about 500,000 ppm of an ester of a polyhydricalcohol and formic acid, or from about 10 ppm to about 500,000 ppm of anester of a polyhydric alcohol and formic acid. For example, the firstreagent in the formed liquid can comprise from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the first reagent in theformed liquid can comprise from about 50 ppm to about 40,000 ppm of anester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

In another example, the solid composition of the peroxyformic acidforming composition can comprise any suitable concentration of an esterof a polyhydric alcohol and formic acid. In some embodiments, the solidcomposition can provide a concentrate formed liquid that comprises thefirst reagent in an amount up to about 90% of an ester of a polyhydricalcohol and formic acid. In other embodiments, the solid composition canprovide for the formed liquid from about 10 ppm to about 500,000 ppm ofan ester of a polyhydric alcohol and formic acid. For example, the solidcomposition can provide for the formed liquid the ester of a polyhydricalcohol and formic acid in amounts comprising from about 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm,5,500-6,000 ppm, 6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm,7,500-8,000 ppm, 8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm,10,000-20,000 ppm, 20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000ppm, 50,000-60,000 ppm, 60,000-70,000 ppm, 70,000-80,000 ppm,80,000-90,000 ppm, 90,000-100,000 ppm, 100,000-150,000 ppm,150,000-200,000 ppm, 200,000-250,000 ppm, 250,000-300,000 ppm,300,000-350,000 ppm, 350,000-400,000 ppm, 400,000-450,000 ppm, or450,000-500,000 ppm. In other embodiments, the solid composition canprovide for the formed liquid from about 50 ppm to about 40,000 ppm ofan ester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

The present peroxyformic acid forming compositions can comprise anysuitable concentration of hydrogen peroxide or a substance thatgenerates hydrogen peroxide upon contact with a liquid. For example, thesecond reagent of the peroxyformic acid forming composition can compriseany suitable concentration of hydrogen peroxide. In some embodiments, aconcentrate formed liquid comprises the second reagent in an amount upto about 10% of hydrogen peroxide. In some embodiments, the formedliquid comprises the second reagent in an amount comprising about 0.1ppm to about 100,000 ppm of hydrogen peroxide, or about 0.1 ppm to about100,000 ppm of hydrogen peroxide. For example, the second reagent in theformed liquid can comprise from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm, 100,000-150,000 ppm, 150,000-200,000 ppm,200,000-250,000 ppm, or 250,000-300,000 ppm hydrogen peroxide. In otherembodiments, the second reagent in the formed liquid comprises fromabout 150 ppm to about 50,000 ppm of hydrogen peroxide, e.g., about150-200, 150-300, 150-400, 150-500, 150-600, 150-700, 150-800, 150-900,150-1,000, 150-1,500, 150-2,000, 150-2,500, 150-3,000, 150-3,500,150-4,000, 150-4,500, 150-5,000, 150-10,000, 50-20,000, 50-30,000,50-40,000 or 50-50,000 ppm of hydrogen peroxide.

In some embodiments, a concentrate formed liquid comprises the secondreagent in an amount up to about 10% of hydrogen peroxide. In anotherexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1 ppm to about 100,000 ppm ofhydrogen peroxide upon contact with a liquid in the formed liquid. Forexample, the solid composition can comprise a substance at an amount orconcentration that generates from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm,20,000-30,000 ppm, 30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000ppm, 60,000-70,000 ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or90,000-100,000 ppm hydrogen peroxide.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. For example, the first reagent andthe second reagent in the present peroxyformic acid forming compositionscan be configured to be contacted with each other to form a liquidand/or solid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. In some embodiments, the firstreagent and the second reagent can be configured to be contacted witheach other to form a liquid, e.g., a solution, that comprises from about0.1 ppm to about 100,000 ppm of peroxyformic acid, from about 0.1 ppm toabout 10,000 ppm of peroxyformic acid, or from about 0.1 ppm to about5,000 ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm or greater ofperoxyformic acid. In other embodiments, the first reagent and thesecond reagent can be configured to be contacted with each other to forma liquid, e.g., a solution, that comprises from about 1 ppm to about 500ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm,0.1-30 ppm, 0.1-40 ppm, 0.1-50 ppm, 0.1-60 ppm, 0.1-70 ppm, 0.1-80 ppm,0.1-90 ppm, 0.1-100 ppm, 0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0.1-300ppm, 0.1-350 ppm, 0.1-400 ppm, 0.1-450 ppm, 0.1-500 ppm of peroxyformicacid. In still other embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises from about 50 ppm to about 100ppm of peroxyformic acid, e.g., about 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm or 90-100 ppm of peroxyformic acid. In yet other embodiments,the first reagent and the second reagent can be configured to becontacted with each other to form a liquid, e.g., a solution, thatcomprises from about 200 ppm to about 300 ppm of peroxyformic acid,e.g., about 200-210 ppm, 210-220 ppm, 220-230 ppm, 230-240 ppm, 240-250ppm, 250-260 ppm, 260-270 ppm, 270-280 ppm, 280-290 ppm, 290-300 ppm ofperoxyformic acid.

In another example, the solid composition can be configured to becontacted with a liquid to form a solution that comprises from about 0.1ppm to about 100,000 ppm of peroxyformic acid, from about 0.1 ppm toabout 10,000 ppm of peroxyformic acid, or from about 0.1 ppm to about5,000 ppm of peroxyformic acid. In some embodiments, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises from about 0.1 ppm to about5,000 ppm of peroxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm,80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm,550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm,1,500-2,000 ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm,3,500-4,000 ppm, 4,000-4,500 ppm, or 4,500-5,000 ppm or greater ofperoxyformic acid.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid within any suitable time. Forexample, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid and/or solid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 1 ppmperoxyformic acid within 1 minute of the contact time, e.g., at leastabout 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm or greaterof peroxyformic acid within 1 minute of the contact time.

In another example, the solid composition can be configured to becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises at least about 1 ppm peroxyformic acid within 1minute of the contact time, e.g., at least about 1 ppm, 2 ppm, 3 ppm, 4ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm,30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm,75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm,3,000 ppm, 4,000 ppm, or 5,000 ppm or greater, of peroxyformic acidwithin 1 minute of the contact time.

In an aspect, at least about 1 ppm peroxyformic is generated within lessthan 1 minute of contacting the first reagent and the second reagent. Inan aspect, at least about 1 ppm peroxyformic is generated within lessthan about 55 seconds, 50 seconds or less, 45 seconds or less, 40seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds orless, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5seconds or less. In an aspect, the reaction to form a liquid comprisingat least about 1 ppm peroxyformic acid is near instantaneous.

In an aspect, at least about 100 ppm or at least about 500 ppmperoxyformic is generated within about 5 minutes or less of contactingthe first reagent and the second reagent. In an aspect, at least about100 ppm or 500 ppm peroxyformic is generated within less than about 4minutes, 3 minutes or less, 2 minutes or less, or 1 minute or less.

The present peroxyformic acid forming compositions can be configured toform a liquid, e.g., a solution, that comprises any suitable percentageof the peak concentration of peroxyformic acid within any suitable time.For example, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid, e.g., a solution, that comprises anysuitable percentage of the peak concentration of peroxyformic acidwithin any suitable time. In some embodiments, the first reagent and thesecond reagent are configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 80% of the peakconcentration of peroxyformic acid within from about 5 minutes to about15 minutes of the contact time. For example, the first reagent and thesecond reagent are configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 80%, 85%, 90%,95%, 96%, 97%, 98%, 99% or 100% of the peak concentration ofperoxyformic acid within from about 5 minutes to about 15 minutes of thecontact time. In another example, the first reagent and the secondreagent are configured to be contacted with each other to form a liquid,e.g., a solution, that comprises at least about 80% of the peakconcentration of peroxyformic acid within from about 5, 6, 7, 8, 9, 10,11, 12, 13, 14 or 15 minutes of the contact time.

In another example, the solid composition can be configured to becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises any suitable percentage of the peak concentration ofperoxyformic acid within any suitable time. In some embodiments, thesolid composition can be configured to be contacted with a liquid toform a liquid, e.g., a solution, that comprises at least about 80% ofthe peak concentration of peroxyformic acid within from about 5 minutesto about 15 minutes of the contact time. For example, the solidcomposition can be configured to be contacted with a liquid to form aliquid, e.g., a solution, that comprises at least about 80%, 85%, 90%,95%, 96%, 97%, 98%, 99% or 100% of the peak concentration ofperoxyformic acid within from about 5 minutes to about 15 minutes of thecontact time. In another example, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises at least about 80% of the peak concentration ofperoxyformic acid within from about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or15 minutes of the contact time.

The formed peroxyformic acid can maintain any suitable percentage of thepeak concentration of peroxyformic acid within any suitable time. Insome embodiments, the formed peroxyformic acid can maintain at leastabout 50% of the peak concentration from about 5 minutes to about 25minutes after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.For example, the formed peroxyformic acid can maintain at least about50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or100% of the peak concentration from about 5 minutes to about 25 minutesafter the contact between the first reagent and the second reagent orafter the contact between the solid composition and a liquid. In anotherexample, the formed peroxyformic acid can maintain at least about 50% ofthe peak concentration from about 5-25 minutes, e.g., about 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25minutes, after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.

In some embodiments, the first reagent and the second reagent of thepresent peroxyformic acid forming composition are configured to becontacted with each other to form a solution that comprises at leastabout 80% of the peak concentration of peroxyformic acid within fromabout 1 minute to about 15 minutes of the contact time. In otherembodiments, the formed peroxyformic acid maintains at least about 50%of the peak concentration from about 1 minute to about 15 minutes afterthe contact between the first reagent and the second reagent. In stillother embodiments, the solid composition can be configured to becontacted with a liquid to form a solution that comprises at least about80% of the peak concentration of peroxyformic acid within from about 1minute to about 15 minutes of the contact time. In other embodiments,the formed peroxyformic acid maintains at least about 50% of the peakconcentration from about 1 minute to about 15 minutes after the contactbetween the solid composition and the liquid.

In preferred aspects of the invention the desired peak concentration ofperoxyformic acid is 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, 5,000ppm, 6,000 ppm, 7,000 ppm, 8,000 ppm, 9,000 ppm, 10,000 ppm or more(inclusive of any ranges therein).

The present peroxyformic acid forming compositions can further comprisea C₂-C₂₂ percarboxylic acid, and wherein the first reagent or the solidcomposition comprising the first reagent and the second reagent are keptseparately from the C₂-C₂₂ percarboxylic acid prior to generateperoxyformic acid. The present peroxyformic acid forming compositionscan comprise any suitable C₂-C₂₂ percarboxylic acid, e.g., peroxyaceticacid, peroxyoctanoic acid and/or peroxysulfonated oleic acid.

In some embodiments, the present peroxyformic acid forming compositionsdo not comprise a perhyrolysis enzyme. For example, in some cases, thepresent peroxyformic acid forming compositions do not comprise a memberof family 7 of the carbohydrate esterases (CE-7) or a perhyrolysisenzyme that is disclosed in U.S. patent application 2013/0289113.

Methods for Forming Peroxyformic Acid

In another aspect, the present invention is directed to a method forforming peroxyformic acid comprising: a) contacting a first reagent thatcomprises an ester of a polyhydric alcohol and formic acid, and a secondreagent that comprises hydrogen peroxide or that comprises a substancethat generates hydrogen peroxide when in contact with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, orfrom −2 to about 11, or from 0 to about 11 (or any range therein),wherein said first reagent and said second reagent are kept separatelyprior to said contacting and pH of said formed liquid becomes about 8 orlower within about 1 minute after the contact between said first reagentand said second reagent; or b) contacting a solid composition thatcomprises a first reagent that comprises an ester of a polyhydricalcohol and formic acid, and a second reagent that comprises a substancethat generates hydrogen peroxide when in contact with a liquid with aliquid to form a liquid that comprises peroxyformic acid and has a pHbelow about 11, or from −2 to about 11, or from 0 to about 11, and pH ofsaid formed liquid becomes about 8 or lower within about 1 minute afterthe contact between said solid composition and said liquid.

In some embodiments, the present methods comprise contacting a firstreagent that comprises an ester of a polyhydric alcohol and formic acid,and a second reagent that comprises hydrogen peroxide or that comprisesa substance that generates hydrogen peroxide when in contact with aliquid to form a liquid that comprises peroxyformic acid and has a pHbelow about 11, or from −2 to about 11, or from 0 to about 11 (or anyrange therein), wherein said first reagent and said second reagent arekept separately prior to said contacting and pH of said formed liquidbecomes about 8 or lower within about 1 minute after the contact betweensaid first reagent and said second reagent. In other embodiments, thepresent methods comprise contacting a solid composition that comprises afirst reagent that comprises an ester of a polyhydric alcohol and formicacid, and a second reagent that comprises a substance that generateshydrogen peroxide when in contact with a liquid with a liquid to form aliquid that comprises peroxyformic acid and has a pH below about 11, orfrom −2 to about 11, or from 0 to about 11, and pH of said formed liquidbecomes about 8 or lower within about 1 minute after the contact betweensaid solid composition and said liquid.

Any suitable ester of a polyhydric alcohol and formic acid can be usedin the present methods. Typically, a polyhydric alcohol refers to amolecule with two or more hydroxyl (—OH) groups. An ester of apolyhydric alcohol and formic acid refers to an ester formed between apolyhydric alcohol and formic acid. In some embodiments, glycerolformates, pentaerythritol formates, mannitol formates, propylene glycolformates, sorbitol formates and sugar formates can be used in thepresent methods. Any suitable sugar formates can be used in the presentmethods, e.g., sucrose formates, dextrin formates, maltodextrinformates, or starch formates.

The first reagent or second reagent used in the present methods can haveany suitable pH range. For example, the first reagent or second reagentcan have a pH below about 11, or from −2 to about 11, or from about 0 toabout 11, e.g., about −2 to about −1, −1-0, 0-1, 0-2, 0-3, 0-4, 0-5,0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9,1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5,3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11,5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11, 6-7, 7-8,7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or at about −2, −1,0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11. In some embodiments, the firstreagent or second reagent has a pH ranging from about 5 to about 10,e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9,7-10, 8-9, 8-10, or 9-10. In other embodiments, the first reagent orsecond reagent has a pH at about 9.

The first reagent and the second reagent can be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid and has any suitable pH below about 11, or from −2 to about 11, orfrom about 0 to about 11, e.g., about −2 to about −1, −1-0, 0-1, 0-2,0-3, 0-4, 0-5, 0-6, 0-7, 0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6,1-7, 1-8, 1-9, 1-10, 1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10,2-11, 3-4, 3-5, 3-6, 3-7, 3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9,4-10, 4-11, 5-6, 5-7, 5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11,6-7, 7-8, 7-9, 7-10, 7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or atabout −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 or 11.

In some embodiments, the first reagent and the second reagent arecontacted with each other to form a liquid, e.g., a solution, thatcomprises peroxyformic acid and has a pH ranging from about 5 to about10, e.g., about 5-6, 5-7, 5-8, 5-9, 5-10, 6-7, 6-8, 6-9, 6-10, 7-8, 7-9,7-10, 8-9, 8-10, or 9-10. In other embodiments, the first reagent andthe second reagent are contacted with each other to form a liquid, e.g.,a solution, that comprises peroxyformic acid and has a pH at about 9.The a solid composition can be contacted with a liquid to form a liquid,e.g., a solution, that comprises peroxyformic acid and has any suitablepH below about 11, or from −2 to about 11, or from about 0 to about 11,e.g., about −2 to about −1, −1-0, 0-1, 0-2, 0-3, 0-4, 0-5, 0-6, 0-7,0-8, 0-9, 0-10, 0-11, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7, 1-8, 1-9, 1-10,1-11, 2-3, 2-4, 2-5, 2-6, 2-7, 2-8, 2-9, 2-10, 2-11, 3-4, 3-5, 3-6, 3-7,3-8, 3-9, 3-10, 3-11, 4-5, 4-6, 4-7, 4-8, 4-9, 4-10, 4-11, 5-6, 5-7,5-8, 5-9, 5-10, 5-11, 6-7, 6-8, 6-9, 6-10, 6-11, 6-7, 7-8, 7-9, 7-10,7-11, 8-9, 8-10, 8-11, 9-10, 9-11, 10-11, or at about −2, −1, 0, 1, 2,3, 4, 5, 6, 7, 8, 9, 10 or 11. The pH of the formed liquid can becomeabout 8 or lower within about 1 minute after the contact between thefirst reagent and the second reagent or after the contact between thesolid composition and the liquid. In some embodiments, the pH of theformed liquid can become about 8 or lower within about 1 second, 2seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7 seconds, 8seconds, 9 seconds, 10 seconds, 20 seconds, 30 seconds, 40 seconds, 50seconds after the contact between the first reagent and the secondreagent or after the contact between the solid composition and theliquid. In other embodiments, the pH of the formed liquid can becomeabout lower than 0, 0, 1, 2, 3, 4, 5, 6, 7, 8 within about 1 minuteafter the contact between the first reagent and the second reagent orafter the contact between the solid composition and the liquid. In anaspect, the pH of the formed liquid comprising peroxyformic acid becomesabout 8 or lower within about 1 minute or less. In an aspect, the pH ofthe formed liquid comprising peroxyformic acid becomes about 8 or lowerwithin about 45 seconds or less, 40 seconds or less, 35 seconds or less,30 seconds or less, 25 seconds or less, 20 seconds or less, 15 secondsor less, 10 seconds or less, or 5 seconds or less. In an aspect, the pHof the formed liquid comprising peroxyformic acid becomes about 8 orlower near instantaneously.

The liquid that comprises peroxyformic acid can maintain the pH rangingfrom about 0 to about 8 for any suitable time after the contact betweenthe first reagent and the second reagent, or after the contact betweenthe composition and a liquid. In some embodiments, the liquid thatcomprises peroxyformic acid maintains the pH ranging from about −2 toabout 11, about 0 to about 11, or 0 to about 8 from about 1 second toabout 10 hours after the contact between the first reagent and thesecond reagent or after the contact between the composition and aliquid. For example, the liquid that comprises peroxyformic acid canmaintain the pH at about −2, −1, 0, 1, 2, 3, 4, 5, 6, 7, or 8 from about1 second to about 10 hours after the contact between the first reagentand the second reagent or after the contact between the composition anda liquid. In another example, the liquid that comprises peroxyformicacid can maintain the pH ranging from about 0 to about 8 for about 1second, 2 seconds, 3 seconds, 4 seconds, 5 seconds, 6 seconds, 7seconds, 8 seconds, 9 seconds, 10 seconds, 20 seconds, 30 seconds, 40seconds, 50 seconds, 1 minute, 2 minutes, 3 minutes, 4 minutes, 5minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, 20minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2 hours, 3 hours, 4hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or 10 hours.

In some embodiments, the first reagent and the second reagent can becontacted with each other to form a solution that comprises peroxyformicacid and has a pH ranging from about 4 to about 8 or 9, e.g., about 4-5,5-6, 6-7, 7-8, or 8-9. In one example, the first reagent and the secondreagent are contacted with each other to form a solution that comprisesperoxyformic acid and has a pH ranging from about 6 to about 8 or 9. Thefirst reagent and the second reagent can be contacted with each other toform a solution that comprises peroxyformic acid and has a pH rangingfrom about 4 to about 8 or 9, and the solution can maintain the pH rangefor any suitable amount of time, e.g., from about 1 minute to about 24hours. For example, the solution can maintain the pH range from about 4to about 8 or 9 for at least about 1 minute, 2 minutes, 3 minutes, 4minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1 hour, 2hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, or10 hours.

In other embodiments, the solid composition can be contacted with aliquid to form a solution that comprises peroxyformic acid and has a pHranging from about 4 to about 8 or 9, e.g., about 4-5, 5-6, 6-7, 7-8, or8-9. In one example, the solid composition is contacted with a liquid toform a solution that comprises peroxyformic acid and has a pH rangingfrom about 6 to about 8 or 9. The solid composition can be contactedwith a liquid to form a solution that comprises peroxyformic acid andhas a pH ranging from about 4 to about 8 or 9, and the solution canmaintain the pH range for any suitable amount of time, e.g., from about1 minute to about 24 hours. For example, the solution can maintain thepH range from about 4 to about 8 or 9 for at least about 1 minute, 2minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8minutes, 9 minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50minutes, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8hours, 9 hours, or 10 hours.

The first reagent and the second reagent can be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid under any suitable conditions or temperature. In some embodiments,the first reagent and the second reagent can be contacted with eachother to form a liquid, e.g., a solution, that comprises peroxyformicacid under ambient conditions. In other embodiments, the first reagentand the second reagent can be contacted with each other to form aliquid, e.g., a solution, that comprises peroxyformic acid at atemperature ranging from about −2° C. to about 60° C., 0° C. to about60° C., or 4° C. to about 60° C., e.g., about −2° C.-0° C., 0° C.-4° C.,4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C.,25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50°C., 50° C.-55° C., or 55° C.-60° C. In still other embodiments, thefirst reagent and the second reagent can be contacted with each other toform a liquid, e.g., a solution, that comprises peroxyformic acid at atemperature at about 4° C. or lower than 4° C., e.g., at about 3° C., 2°C., 1° C., 0° C., or lower than 0° C.

The solid composition can be contacted with a liquid to form a liquid,e.g., a solution, that comprises peroxyformic acid under any suitableconditions or temperature. In some embodiments, the solid compositioncan be contacted with a liquid to form a liquid, e.g., a solution, thatcomprises peroxyformic acid under ambient conditions. In otherembodiments, the solid composition can be contacted with a liquid toform a liquid, e.g., a solution, that comprises peroxyformic acid at atemperature ranging from about −2° C. to about 60° C., 0° C. to about60° C., or 4° C. to about 60° C., e.g., about −2° C.-0° C., 0° C.-4° C.,4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C.,25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50°C., 50° C.-55° C., or 55° C.-60° C. In still other embodiments, thesolid composition can be contacted with a liquid to form a liquid, e.g.,a solution, that comprises peroxyformic acid at a temperature at about4° C. or lower than 4° C., e.g., at about 3° C., 2° C., 1° C., 0° C., orlower than 0° C.

The present methods can further comprise using a catalyst or an enzymethat catalyzes formation of peroxyformic acid from the ester of apolyhydric alcohol and formic acid, and hydrogen peroxide. The presentmethods can use any suitable catalyst or enzyme, e.g., a perhydrolyticenzyme, lipase, coronase, termanyl or esperease. The catalyst or anenzyme can be comprised in any suitable reagent. In some embodiments,the first reagent comprises the catalyst or enzyme. In otherembodiments, the second reagent comprises the catalyst or enzyme. Instill other embodiments, the present methods can further comprise usinga third reagent that comprises the catalyst or enzyme. In yet otherembodiments, the solid composition comprises the catalyst or enzyme.

The present methods can further comprise using a stabilizing agent forperoxyformic acid, a stabilizing agent for hydrogen peroxide, and/or apH buffering agent. The present methods can use any suitable stabilizingagent. Exemplary stabilizing agents include a phosphonate salt(s) and/ora heterocyclic dicarboxylic acid, e.g., dipicolinic acid. In someembodiments, the stabilizing agent is pyridine carboxylic acid basedstabilizers, such as picolinic acid and salts, pyridine-2,6-dicarboxylicacid and salts, and phosphonate based stabilizers, such as phosphoricacid and salts, pyrophosphoric acid and salts and most commonly1-hydroxyethylidene-1,1-diphosphonic acid (HEDP) and salts. In otherembodiments, the present methods can use two or more stabilizing agents,e.g., HEDP and 2,6-pyridinedicarboxylic acid (DPA).

The stabilizing agent(s) can be comprised in any suitable reagent. Insome embodiments, the first reagent comprises a stabilizing agent forperoxyformic acid and/or a pH buffering agent. In other embodiments, thesecond reagent comprises a stabilizing agent for hydrogen peroxide. Instill other embodiments, the present methods can further comprise usinga third reagent that comprises a stabilizing agent for peroxyformicacid, a stabilizing agent for hydrogen peroxide, and/or a pH bufferingagent. In yet other embodiments, the solid composition comprises astabilizing agent for peroxyformic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent.

The present methods can use any suitable pH buffering agent. The pHbuffer reagent can include any reagent that is compatible with theester(s) used in the present methods. Exemplary buffer agents suitablefor using with a liquid ester can be an organic amine, such astriethanol amine, imidazole, etc. Exemplary buffer agents suitable forusing with a solid form of ester include a broader range of buffers,such as a carbonate salt, a phosphate salt, etc. The pH buffer reagentcan be comprised in any suitable reagent. In some embodiments, the firstreagent comprises a pH buffering agent. In other embodiments, the solidcomposition comprises a pH buffering agent.

The present methods can use any suitable stabilizing agent for hydrogenperoxide. Exemplary stabilizing agents for hydrogen peroxide includephosphonates, heterocyclic carboxylic acids and the mixtures thereof. Insome embodiments, stabilizing agents for hydrogen peroxide can beDequest 2010, Dequest 2066, Dipicolinic acids, etc. The stabilizingagent for hydrogen peroxide can be comprised in any suitable reagent. Insome embodiments, the second reagent comprises a stabilizing agent forhydrogen peroxide. In other embodiments, the present methods can furthercomprise using a third reagent that comprises a stabilizing agent forhydrogen peroxide. In still other embodiments, the solid compositioncomprises a stabilizing agent for hydrogen peroxide.

The present methods can use any suitable number of dosage(s) of thefirst reagent that is kept separately prior to use, and is used tocontact the second reagent that comprises hydrogen peroxide. Forexample, the present methods can use a single dosage of the firstreagent that is kept separately prior to use, and is used to contact thesecond reagent that comprises hydrogen peroxide. In another example, thepresent methods can use multiple dosages of the first reagent that arekept separately prior to use, and are used to contact the second reagentthat comprises hydrogen peroxide, either simultaneously or sequentially.The multiple dosages of the first reagent comprise any suitable ester(s)of a polyhydric alcohol and formic acid. For example, the multipledosages of the first reagent can comprise the same ester of a polyhydricalcohol and formic acid. In another example, the multiple dosages of thefirst reagent can comprise different esters of polyhydric alcohols andformic acid. The multiple dosages of the first reagent can comprise thesame or different concentrations of ester(s) of a polyhydric alcohol andformic acid. In still another example, the present methods can usemultiple dosages of the solid composition that are kept separately priorto use.

The present methods can use any suitable concentration of an ester of apolyhydric alcohol and formic acid. For example, the first reagent ofthe peroxyformic acid forming composition can comprise any suitableconcentration of an ester of a polyhydric alcohol and formic acid. Insome embodiments, the formed liquid is a concentrate and comprises thefirst reagent in an amount up to about 90% of an ester of a polyhydricalcohol and formic acid to form the peroxyformic acid. In someembodiments, the amount of first reagent in the formed liquid togenerate the peroxyformic acid can comprise from about 1 ppm to about500,000 ppm of an ester of a polyhydric alcohol and formic acid, or fromabout 10 ppm to about 500,000 ppm of an ester of a polyhydric alcoholand formic acid. For example, the first reagent in the formed liquid cancomprise from about 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm,400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm,950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm,4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm,6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm,8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm,30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, 90,000-100,000 ppm,100,000-150,000 ppm, 150,000-200,000 ppm, 200,000-250,000 ppm,250,000-300,000 ppm, 300,000-350,000 ppm, 350,000-400,000 ppm,400,000-450,000 ppm, or 450,000-500,000 ppm. In other embodiments, thefirst reagent can comprise from about 50 ppm to about 40,000 ppm of anester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

In another example, the solid composition of the peroxyformic acidforming composition can comprise any suitable concentration of an esterof a polyhydric alcohol and formic acid. In some embodiments, the solidcomposition can provide for the formed liquid a concentrate comprisingup to about 90% of an ester of a polyhydric alcohol and formic acid toform the peroxyformic acid. In some embodiments, the solid compositioncan provide for the formed liquid amounts from about 1 ppm to about500,000 ppm of an ester of a polyhydric alcohol and formic acid, or fromabout 10 ppm to about 500,000 ppm of an ester of a polyhydric alcoholand formic acid. For example, the solid composition can provide for theformed liquid amounts from about 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm,100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm,650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm,4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm,6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm,8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm,30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, 90,000-100,000 ppm,100,000-150,000 ppm, 150,000-200,000 ppm, 200,000-250,000 ppm,250,000-300,000 ppm, 300,000-350,000 ppm, 350,000-400,000 ppm,400,000-450,000 ppm, or 450,000-500,000 ppm. In other embodiments, thesolid composition can comprise sufficient amount of the esters for theformed liquid to comprise from about 50 ppm to about 40,000 ppm of anester of a polyhydric alcohol and formic acid, e.g., 50-100, 50-500,50-1,000, 50-1,500, 50-2,000, 50-2,500, 50-3,000, 50-3,500, 50-4,000,50-4,500, 50-5,000, 50-10,000, 50-20,000, 50-30,000, or 50-40,000 ppm ofan ester of a polyhydric alcohol and formic acid.

The present methods can use any suitable concentration of hydrogenperoxide or a substance that generates hydrogen peroxide upon contactwith a liquid. For example, the second reagent of the peroxyformic acidforming composition can comprise any suitable concentration of hydrogenperoxide. In some embodiments, the second reagent can provide for theformed liquid a concentrate comprising up to about 10% of the hydrogenperoxide. In some embodiments, the formed liquid can comprise the secondreagent in amounts from about 0.1 ppm to about 100,000 ppm of hydrogenperoxide, or from about 1 ppm to about 100,000 ppm of hydrogen peroxide.For example, the second reagent in the formed liquid can comprise fromabout 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm,50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm,150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm,700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm,950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm,4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm,6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm,8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm,30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, or 90,000-100,000 ppmhydrogen peroxide. In other embodiments, the second reagent in theformed liquid comprises from about 150 ppm to about 50,000 ppm ofhydrogen peroxide, e.g., about 150-200, 150-300, 150-400, 150-500,150-600, 150-700, 150-800, 150-900, 150-1,000, 150-1,500, 150-2,000,150-2,500, 150-3,000, 150-3,500, 150-4,000, 150-4,500, 150-5,000,150-10,000, 50-20,000, 50-30,000, 50-40,000 or 50-50,000 ppm of hydrogenperoxide.

In another example, the solid composition can comprise a substance at anamount or concentration that generates from about 0.1 ppm to about100,000 ppm of hydrogen peroxide, or from about 1 ppm to about 100,000ppm of hydrogen peroxide in the formed liquid. For example, the solidcomposition can comprise a substance at an amount or concentration thatgenerates from about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm,100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm,650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm,4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm,6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000 ppm, 8,000-8,500 ppm,8,500-9,000 ppm, 9,000-10,000 ppm, 10,000-20,000 ppm, 20,000-30,000 ppm,30,000-40,000 ppm, 40,000-50,000 ppm, 50,000-60,000 ppm, 60,000-70,000ppm, 70,000-80,000 ppm, 80,000-90,000 ppm, 90,000-100,000 ppm,100,000-150,000 ppm, 150,000-200,000 ppm, 200,000-250,000 ppm, or250,000-300,000 ppm hydrogen peroxide in the formed liquid.

The present methods can be used to form a liquid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid. For example,the first reagent and the second reagent can be contacted with eachother to form a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid. In some embodiments, the firstreagent and the second reagent can be contacted with each other to forma liquid, e.g., a solution, that comprises from about 0.1 ppm to about100,000 ppm of peroxyformic acid, from about 0.1 ppm to about 10,000 ppmof peroxyformic acid or from about 0.1 ppm to about 5,000 ppm ofperoxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm,90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm,600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm,2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, or 4,500-5,000 ppm or greater of peroxyformic acid. Inother embodiments, the first reagent and the second reagent can becontacted with each other to form a liquid, e.g., a solution, thatcomprises from about 1 ppm to about 500 ppm of peroxyformic acid, e.g.,about 0.1-1 ppm, 0.1-10 ppm, 0.1-20 ppm, 0.1-30 ppm, 0.1-40 ppm, 0.1-50ppm, 0.1-60 ppm, 0.1-70 ppm, 0.1-80 ppm, 0.1-90 ppm, 0.1-100 ppm,0.1-150 ppm, 0.1-200 ppm, 0.1-250 ppm, 0.1-300 ppm, 0.1-350 ppm, 0.1-400ppm, 0.1-450 ppm, 0.1-500 ppm of peroxyformic acid. In still otherembodiments, the first reagent and the second reagent can be contactedwith each other to form a liquid, e.g., a solution, that comprises fromabout 50 ppm to about 100 ppm of peroxyformic acid, e.g., about 50-60ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm or 90-100 ppm of peroxyformic acid.In yet other embodiments, the first reagent and the second reagent canbe contacted with each other to form a liquid, e.g., a solution, thatcomprises from about 200 ppm to about 300 ppm of peroxyformic acid,e.g., about 200-210 ppm, 210-220 ppm, 220-230 ppm, 230-240 ppm, 240-250ppm, 250-260 ppm, 260-270 ppm, 270-280 ppm, 280-290 ppm, 290-300 ppm ofperoxyformic acid.

In another example, the solid composition can be contacted with a liquidto form a solution that comprises from about 0.1 ppm to about 100,000ppm of peroxyformic acid, from about 0.1 ppm to about 10,000 ppm ofperoxyformic acid or from about 0.1 ppm to about 5,000 ppm ofperoxyformic acid. In some embodiments, the solid composition can becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises from about 0.1 ppm to about 5,000 ppm of peroxyformic acid,e.g., about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm,400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm,950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm, or4,500-5,000 ppm or greater of peroxyformic acid.

The present methods can be used to form a liquid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. For example, the first reagent and the second reagent inthe present peroxyformic acid forming compositions can be contacted witheach other to form a liquid, e.g., a solution, that comprises anysuitable concentration of peroxyformic acid within any suitable time. Insome embodiments, the first reagent and the second reagent can becontacted with each other to form a liquid, e.g., a solution, thatcomprises at least about 1 ppm peroxyformic acid within 1 minute of thecontact time, e.g., at least about 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm, 3,000ppm, 4,000 ppm, or 5,000 ppm or greater, of peroxyformic acid within 1minute of the contact time.

In another example, the solid composition can be contacted with a liquidto form a liquid, e.g., a solution, that comprises any suitableconcentration of peroxyformic acid within any suitable time. In someembodiments, the solid composition can be contacted with a liquid toform a liquid, e.g., a solution, that comprises at least about 1 ppmperoxyformic acid within 1 minute of the contact time, e.g., at leastabout 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm orgreater, of peroxyformic acid within 1 minute of the contact time.

In an aspect, at least about 1 ppm peroxyformic is generated within lessthan 1 minute of contacting the first reagent and the second reagent. Inan aspect, at least about 1 ppm peroxyformic is generated within lessthan about 55 seconds, 50 seconds or less, 45 seconds or less, 40seconds or less, 35 seconds or less, 30 seconds or less, 25 seconds orless, 20 seconds or less, 15 seconds or less, 10 seconds or less, or 5seconds or less. In an aspect, the reaction to form a liquid comprisingat least about 1 ppm peroxyformic acid is near instantaneous.

In an aspect, at least about 100 ppm or at least about 500 ppmperoxyformic is generated within about 5 minutes or less of contactingthe first reagent and the second reagent. In an aspect, at least about100 ppm or 500 ppm peroxyformic is generated within less than about 4minutes, 3 minutes or less, 2 minutes or less, or 1 minute or less.

The present methods can be used to form a liquid, e.g., a solution, thatcomprises any suitable percentage of the peak concentration ofperoxyformic acid within any suitable time. For example, the firstreagent and the second reagent can be contacted with each other to forma liquid, e.g., a solution, that comprises any suitable percentage ofthe peak concentration of peroxyformic acid within any suitable time. Insome embodiments, the first reagent and the second reagent are contactedwith each other to form a liquid, e.g., a solution, that comprises atleast about 80% of the peak concentration of peroxyformic acid withinfrom about 5 minutes to about 15 minutes of the contact time. Forexample, the first reagent and the second reagent are contacted witheach other to form a liquid, e.g., a solution, that comprises at leastabout 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or 100% of the peakconcentration of peroxyformic acid within from about 5 minutes to about15 minutes of the contact time. In another example, the first reagentand the second reagent are contacted with each other to form a liquid,e.g., a solution, that comprises at least about 80% of the peakconcentration of peroxyformic acid within from about 5, 6, 7, 8, 9, 10,11, 12, 13, 14 or 15 minutes of the contact time.

In another example, the solid composition can be contacted with a liquidto form a liquid, e.g., a solution, that comprises any suitablepercentage of the peak concentration of peroxyformic acid within anysuitable time. In some embodiments, the solid composition can becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises at least about 80% of the peak concentration of peroxyformicacid within from about 5 minutes to about 15 minutes of the contacttime. For example, the solid composition can be contacted with a liquidto form a liquid, e.g., a solution, that comprises at least about 80%,85%, 90%, 95%, 96%, 97%, 98%, 99% or 100% of the peak concentration ofperoxyformic acid within from about 5 minutes to about 15 minutes of thecontact time. In another example, the solid composition can be contactedwith a liquid to form a liquid, e.g., a solution, that comprises atleast about 80% of the peak concentration of peroxyformic acid withinfrom about 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 minutes of thecontact time.

The formed peroxyformic acid can maintain any suitable percentage of thepeak concentration of peroxyformic acid within any suitable time. Insome embodiments, the formed peroxyformic acid can maintain at leastabout 50% of the peak concentration from about 5 minutes to about 25minutes after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.For example, the formed peroxyformic acid can maintain at least about50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99% or100% of the peak concentration from about 5 minutes to about 25 minutesafter the contact between the first reagent and the second reagent orafter the contact between the solid composition and a liquid. In anotherexample, the formed peroxyformic acid can maintain at least about 50% ofthe peak concentration from about 5-25 minutes, e.g., about 5, 6, 7, 8,9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 or 25minutes, after the contact between the first reagent and the secondreagent or after the contact between the solid composition and a liquid.

In some embodiments, the first reagent and the second reagent used inthe present methods can be contacted with each other to form a solutionthat comprises at least about 80% of the peak concentration ofperoxyformic acid within from about 1 minute to about 15 minutes of thecontact time. In other embodiments, the formed peroxyformic acidmaintains at least about 50% of the peak concentration from about 1minute to about 15 minutes after the contact between the first reagentand the second reagent. In still other embodiments, the solidcomposition can be contacted with a liquid to form a solution thatcomprises at least about 80% of the peak concentration of peroxyformicacid within from about 1 minute to about 15 minutes of the contact time.In other embodiments, the formed peroxyformic acid maintains at leastabout 50% of the peak concentration from about 1 minute to about 15minutes after the contact between the solid composition and the liquid.

In preferred aspects of the invention the desired peak concentration ofperoxyformic acid is 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, 5,000ppm, 6,000 ppm, 7,000 ppm, 8,000 ppm, 9,000 ppm, 10,000 ppm or more(inclusive of any ranges therein).

The present methods can further comprise forming a C₂-C₂₂ percarboxylicacid in a liquid, e.g., a solution. The C₂-C₂₂ percarboxylic acid can beany suitable C₂-C₂₂ percarboxylic acid. Exemplary C₂-C₂₂ percarboxylicacid includes peroxyacetic acid, peroxyoctanoic acid and/orperoxysulfonated oleic acid. In some embodiments, the C₂-C₂₂percarboxylic acid is peroxyacetic acid.

The present methods can be used to generate peroxyformic acid in anysuitable manner or at any suitable location. In some embodiments, thepresent methods can be used to generate peroxyformic acid in situ forthe application of the formed peroxyformic acid.

In some embodiments, the present methods do not comprise using aperhyrolysis enzyme. For example, in some cases, the present methods donot comprise using a member of family 7 of the carbohydrate esterases(CE-7) or a perhyrolysis enzyme that is disclosed in U.S. patentapplication 2013/0289113.

In another aspect, the present invention is directed to peroxyformicacid formed using the present methods, e.g., peroxyformic acid formed insitu for the application of the formed peroxyformic acid.

The peroxyformic acid formed using the present methods (presentcomposition) can further comprise additional percarboxylic acids.Various embodiments of the invention referring to peroxyformic acidcompositions and/or peroxyformic acid solutions are further understoodto optionally comprise additional percarboxylic acids. As used herein,the term “peracid” may also be referred to as a “percarboxylic acid” or“peroxyacid.” Sulfoperoxycarboxylic acids, sulfonated peracids andsulfonated peroxycarboxylic acids are also included within the term“peracid” as used herein. The terms “sulfoperoxycarboxylic acid,”“sulfonated peracid,” or “sulfonated peroxycarboxylic acid” refers tothe peroxycarboxylic acid form of a sulfonated carboxylic acid asdisclosed in U.S. Patent Publication Nos. 2010/0021557, 2010/0048730 and2012/0052134 which are incorporated herein by reference in theirentireties. A peracid refers to an acid having the hydrogen of thehydroxyl group in carboxylic acid replaced by a hydroxy group. Oxidizingperacids may also be referred to herein as peroxycarboxylic acids.

In some embodiments, peroxyformic acid with other peroxycarboxylic acidscan be generated by mixing an ester of a polyhydric alcohol with acomposition comprising peroxycaboxylic acid(s) and hydrogen peroxide toform a composition that comprises both peroxyformic acid and otherperoxycarboxylic acids. Examples of compositions comprising bothperoxycarboxylic acid and hydrogen peroxide include peroxyacetic acidcompositions, peroxyoctanoic acid compositions, etc., all arecommercially available from Ecolab Inc. In use, an ester of a polyhydricalcohol can be contacted, e.g., mixed, with Oxonia Active, Tsunami 100,Matrixx, TurboOxysan and Octave, etc., to form a composition thatcomprises both peroxyformic acid and other desired peroxycarboxylicacids.

A peracid includes any compound of the formula R—(COOOH)_(n) in which Rcan be hydrogen, alkyl, alkenyl, alkyne, acylic, alicyclic group, aryl,heteroaryl, or heterocyclic group, and n is 1, 2, or 3, and named byprefixing the parent acid with peroxy. Preferably R includes hydrogen,alkyl, or alkenyl. The terms “alkyl,” “alkenyl,” “alkyne,” “acylic,”“alicyclic group,” “aryl,” “heteroaryl,” and “heterocyclic group” are asdefined herein.

As used herein, the term “alkyl” includes a straight or branchedsaturated aliphatic hydrocarbon chain having from 1 to 22 carbon atoms,such as, for example, methyl, ethyl, propyl, isopropyl (1-methylethyl),butyl, tert-butyl (1,1-dimethylethyl), and the like. The term “alkyl” or“alkyl groups” also refers to saturated hydrocarbons having one or morecarbon atoms, including straight-chain alkyl groups (e.g., methyl,ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.),cyclic alkyl groups (or “cycloalkyl” or “alicyclic” or ‘carbocyclic”groups) (e.g., cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl,cyclooctyl, etc.), branched-chain alkyl groups (e.g., isopropyl,tert-butyl, sec-butyl, isobutyl, etc.), and alkyl-substituted alkylgroups (e.g., alkyl-substituted cycloalkyl groups andcycloalkyl-substituted alkyl groups).

Unless otherwise specified, the term “alkyl” includes both“unsubstituted alkyls” and “substituted alkyls.” As used herein, theterm “substituted alkyls” refers to alkyl groups having substituentsreplacing one or more hydrogens on one or more carbons of thehydrocarbon backbone. Such substituents may include, for example,alkenyl, alkynyl, halogeno, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy,alkoxycarbonyloxy, aryloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl,phosphate, phosphonato, phosphinato, cyano, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino),acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyland ureido), imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate,sulfates, alkylsulfinyl, sulfonates, sulfamoyl, sulfonamido, nitro,trifluoromethyl, cyano, azido, heterocyclic, alkylaryl, or aromatic(including heteroaromatic) groups.

The term “alkenyl” includes an unsaturated aliphatic hydrocarbon chainhaving from 2 to 12 carbon atoms, such as, for example, ethenyl,1-propenyl, 2-propenyl, 1-butenyl, 2-methyl-1-propenyl, and the like.The alkyl or alkenyl can be terminally substituted with a heteroatom,such as, for example, a nitrogen, sulfur, or oxygen atom, forming anaminoalkyl, oxyalkyl, or thioalkyl, for example, aminomethyl, thioethyl,oxypropyl, and the like. Similarly, the above alkyl or alkenyl can beinterrupted in the chain by a heteroatom forming an alkylaminoalkyl,alkylthioalkyl, or alkoxyalkyl, for example, methylaminoethyl,ethylthiopropyl, methoxymethyl, and the like.

Further, as used herein the term “alicyclic” includes any cyclichydrocarbyl containing from 3 to 8 carbon atoms. Examples of suitablealicyclic groups include cyclopropanyl, cyclobutanyl, cyclopentanyl,etc. The term “heterocyclic” includes any closed ring structuresanalogous to carbocyclic groups in which one or more of the carbon atomsin the ring is an element other than carbon (heteroatom), for example, anitrogen, sulfur, or oxygen atom. Heterocyclic groups may be saturatedor unsaturated. Examples of suitable heterocyclic groups include forexample, aziridine, ethylene oxide (epoxides, oxiranes), thiirane(episulfides), dioxirane, azetidine, oxetane, thietane, dioxetane,dithietane, dithiete, azolidine, pyrrolidine, pyrroline, oxolane,dihydrofuran, and furan. Additional examples of suitable heterocyclicgroups include groups derived from tetrahydrofurans, furans, thiophenes,pyrrolidines, piperidines, pyridines, pyrrols, picoline, coumaline, etc.

In some embodiments, alkyl, alkenyl, alicyclic groups, and heterocyclicgroups can be unsubstituted or substituted by, for example, aryl,heteroaryl, C₁₋₄ alkyl, C₁₋₄ alkenyl, C₁₋₄ alkoxy, amino, carboxy, halo,nitro, cyano, —SO₃H, phosphono, or hydroxy. When alkyl, alkenyl,alicyclic group, or heterocyclic group is substituted, preferably thesubstitution is C₁₋₄ alkyl, halo, nitro, amido, hydroxy, carboxy,sulpho, or phosphono. In one embodiment, R includes alkyl substitutedwith hydroxy. The term “aryl” includes aromatic hydrocarbyl, includingfused aromatic rings, such as, for example, phenyl and naphthyl. Theterm “heteroaryl” includes heterocyclic aromatic derivatives having atleast one heteroatom such as, for example, nitrogen, oxygen, phosphorus,or sulfur, and includes, for example, furyl, pyrrolyl, thienyl,oxazolyl, pyridyl, imidazolyl, thiazolyl, isoxazolyl, pyrazolyl,isothiazolyl, etc. The term “heteroaryl” also includes fused rings inwhich at least one ring is aromatic, such as, for example, indolyl,purinyl, benzofuryl, etc.

In some embodiments, aryl and heteroaryl groups can be unsubstituted orsubstituted on the ring by, for example, aryl, heteroaryl, alkyl,alkenyl, alkoxy, amino, carboxy, halo, nitro, cyano, —SO₃H, phosphono,or hydroxy. When aryl, aralkyl, or heteroaryl is substituted, preferablythe substitution is C₁₋₄ alkyl, halo, nitro, amido, hydroxy, carboxy,sulpho, or phosphono. In one embodiment, R includes aryl substitutedwith C₁₋₄ alkyl.

Peracids suitable for use include any peroxycarboxylic acids, includingvarying lengths of peroxycarboxylic and percarboxylic acids (e.g. C1-22)that can be prepared from the reaction of an ester of a polyhydricalcohol and formic acid with hydrogen peroxide as described herein.Additional suitable peracids include those of acid-catalyzed equilibriumreaction between a carboxylic acid described above and hydrogenperoxide. A peroxycarboxylic acid can also be prepared by theauto-oxidation of aldehydes or by the reaction of hydrogen peroxide withan acid chloride, acid hydride, carboxylic acid anhydride, or sodiumalcoholate. Alternatively, peracids can be prepared throughnon-equilibrium reactions, which may be generated for use in situ, suchas the methods disclosed in U.S. Pat. Nos. 8,846,107 and 8,877,254 eachtitled “In Situ Generation of Peroxycarboxylic Acids at Alkaline pH, andMethods of Use Thereof,” which are incorporated herein by reference.Preferably a composition of the invention includes peroxyformic acid,peroxyacetic acid, peroxyoctanoic acid, peroxypropionic acid,peroxylactic acid, peroxyheptanoic acid, peroxyoctanoic acid and/orperoxynonanoic acid.

In some embodiments, a peroxycarboxylic acid includes at least onewater-soluble peroxycarboxylic acid in which R includes alkyl of 1-22carbon atoms. For example, in one embodiment, a peroxycarboxylic acidincludes peroxyformic acid and/or peroxyacetic acid. In anotherembodiment, a peroxycarboxylic acid has R that is an alkyl of 1-22carbon atoms substituted with hydroxy. Methods of preparing peroxyaceticacid are known to those of skill in the art including those disclosed inU.S. Pat. No. 2,833,813, which is herein incorporated herein byreference.

In another embodiment, a sulfoperoxycarboxylic acid has the followingformula:

wherein R₁ is hydrogen, or a substituted or unsubstituted alkyl group;R₂ is a substituted or unsubstituted alkylene group; X is hydrogen, acationic group, or an ester forming moiety; or salts or esters thereof.In additional embodiments, a sulfoperoxycarboxylic acid is combined witha single or mixed peroxycarboxylic acid composition, such as asulfoperoxycarboxylic acid with peroxyacetic acid and peroxyoctanoicacid (PSOA/POOA/POAA).

In other embodiments, a mixed peracid is employed, such as aperoxycarboxylic acid including at least one peroxycarboxylic acid oflimited water solubility in which R includes alkyl of 5-22 carbon atomsand at least one water-soluble peroxycarboxylic acid in which R includesalkyl of 1-4 carbon atoms. For example, in one embodiment, aperoxycarboxylic acid includes peroxyacetic acid and at least one otherperoxycarboxylic acid such as those named above. Preferably acomposition of the invention includes peroxyformic acid, peroxyaceticacid and/or peroxyoctanoic acid. Other combinations of mixed peracidsare well suited for use in the current invention.

Advantageously, a combination of peroxycarboxylic acids provides acomposition with desirable antimicrobial activity in the presence ofhigh organic soil loads. The mixed peroxycarboxylic acid compositionsoften provide synergistic micro efficacy. Accordingly, compositions ofthe invention can include a peroxycarboxylic acid, or mixtures thereof.

Various commercial formulations of peracids are available, including forexample, peracetic acid (15%) available from Ecolab Inc. Most commercialperacid solutions state a specific percarboxylic acid concentrationwithout reference to the other chemical components in a use solution.However, it should be understood that commercial products, such asperacetic acid, will also contain the corresponding carboxylic acid(e.g. acetic acid), hydrogen peroxide and water.

Any suitable C₁-C₂₂ percarboxylic acid can be used in the presentcompositions. In some embodiments, the C₁-C₂₂ percarboxylic acid is aC₂-C₂₀ percarboxylic acid. In other embodiments, the C₁-C₂₂percarboxylic is a C₁, C₂, C₃, C₄, C₅, C₆, C₇, C₈, C₉, C₁₀, C₁₁, C₁₂,C₁₃, C₁₄, C₁₅, C₁₆, C₁₇, C₁₈, C₁₉, C₂₀, C₂₁, or C₂₂ carboxylic acid. Instill other embodiments, the C₁-C₂₂ percarboxylic acid comprisesperoxyformic acid, peroxyacetic acid, peroxyoctanoic acid and/orperoxysulfonated oleic acid.

The C₁-C₂₂ percarboxylic acid can be used at any suitable concentration.In some embodiments, the C₁-C₂₂ percarboxylic acid has a concentrationfrom about 1 wt-% to about 40 wt-%. In other embodiments, the C₁-C₂₂percarboxylic acid has a concentration from about 1 wt-% to about 20wt-%. In still other embodiments, the C₁-C₂₂ percarboxylic acid has aconcentration at about 1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%, 6 wt-%, 7wt-%, 8 wt-%, 9 wt-%, 10 wt-%, 11 wt-%, 12 wt-%, 13 wt-%, 14 wt-%, 15wt-%, 16 wt-%, 17 wt-%, 18 wt-%, 19 wt-%, 20 wt-%, 25 wt-%, 30 wt-%, 35wt-%, or 40 wt-%. In yet other embodiments, the C₁-C₂₂ percarboxylicacid has a concentration from about 0.1 ppm to about 10,000 ppm, e.g.,about 0.1-1 ppm, 1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm,50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm,150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm,700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm,950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000 ppm, 2,000-2,500 ppm,2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm, 4,000-4,500 ppm, or4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm, 6,000-6,500 ppm,6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000, 8,000-8,500 ppm,8,500-9,000 ppm, 9,000-9,500 ppm, or 9,500-10,000 ppm.

Additional Optional Materials

The present compositions can optionally include additional ingredientsto enhance the composition for treating various surfaces and targetsaccording to the invention. Additional optional functional ingredientsmay include for example, peracid stabilizers, emulsifiers, corrosioninhibitors and/or descaling agents (i.e. scale inhibitors), surfactantsand/or additional antimicrobial agents for enhanced efficacy (e.g. mixedperacids, biocides), antifoaming agents, anti-redeposition agents,bleaching agents, dispersants, solubility modifiers, wetting agents,metal protecting agents, sequestrants and/or chelating agents,fragrances and/or dyes, rheology modifiers, hydrotropes or couplers,buffers, solvents, acidulants and/or catalysts (e.g. strong mineralacids), additional carboxylic acids, and the like. In an embodiment, noadditional functional ingredients are employed.

Friction Reducers

Friction reducers are used in water or other water-based fluids used inhydraulic fracturing treatments for subterranean well formations inorder to improve permeability of the desired gas and/or oil beingrecovered from the fluid-conductive cracks or pathways created throughthe fracking process. The friction reducers allow the water to be pumpedinto the formations more quickly. Various polymer additives have beenwidely used as friction reducers to enhance or modify thecharacteristics of the aqueous fluids used in well drilling, recoveryand production applications.

Examples of commonly used friction reducers include polyacrylamidepolymers and copolymers. In an aspect, additional suitable frictionreducers may include acrylamide-derived polymers and copolymers, such aspolyacrylamide (sometime abbreviated as PAM), acrylamide-acrylate(acrylic acid) copolymers, acrylic acid-methacrylamide copolymers,partially hydrolyzed polyacrylamide copolymers (PHPA), partiallyhydrolyzed polymethacrylamide, acrylamide-methyl-propane sulfonatecopolymers (AMPS) and the like. Various derivatives of such polymers andcopolymers, e.g., quaternary amine salts, hydrolyzed versions, and thelike, should be understood to be included with the polymers andcopolymers described herein.

Friction reducers are combined with water and/or other aqueous fluids,which in combination are often referred to as “slick water” fluids.Slick water fluids have reduced frictional drag and beneficial flowcharacteristics which enable the pumping of the aqueous fluids intovarious gas- and/or oil-producing areas, including for example forfracturing.

In an aspect of the invention, a friction reducer is present in a usesolution in an amount between about 1 ppm to 1,000 ppm, or from about100 ppm to 1,000 ppm. In a further aspect, a friction reducer is presentin a use solution in an amount of at least about 0.01 wt-% to about 10wt-%, preferably at least about 0.01 wt-% to about 5 wt-%, preferably atleast about 0.01 wt-% to about 1 wt-%, more preferably at least about0.01 wt-% to about 0.5 wt-%, and still more preferably at least about0.01 wt-% to about 0.1 wt-%. Beneficially, the compositions and methodsof the invention do not negatively interfere with friction reducersincluded in an aqueous solution.

Viscosity Enhancers

Viscosity enhancers are additional polymers used in water or otherwater-based fluids used in hydraulic fracturing treatments to provideviscosity enhancement. Natural and/or synthetic viscosity-increasingpolymers may be employed in compositions and methods according to theinvention. Viscosity enhancers may also be referred to as gelling agentsand examples include guar, xanthan, cellulose derivatives andpolyacrylamide and polyacrylate polymers and copolymers, and the like.

In an aspect of the invention, a viscosity enhancer is present in a usesolution in an amount between about 1 ppm to about 1,000 ppm, or fromabout 100 ppm to 1,000 ppm. In a further aspect, a viscosity enhancer ispresent in a use solution in an amount of at least about 0.01 wt-% toabout 10 wt-%, preferably at least about 0.01 wt-% to about 5 wt-%,preferably at least about 0.01 wt-% to about 1 wt-%, at least about 0.01wt-% to about 2 wt-%, preferably at least about 0.01 wt-% to about 1wt-%, preferably at least about 0.01 wt-% to about 0.5 wt-%.Beneficially, the compositions and methods of the invention do notnegatively interfere with viscosity enhancer included in an aqueoussolution

Corrosion Inhibitors

Corrosion inhibitors are additional molecules used in oil and gasrecovery operations. Corrosion inhibitors that may be employed in thepresent disclosure include the exemplary corrosion inhibitors disclosedin U.S. Pat. Nos. 3,909,447, 4,443,609, 5,965,785 and 9,150,793, GB Pat.No. 1,198,734, WO/03/006581, WO04/044266, and WO08/005058, eachincorporated herein by reference in their entireties.

In some embodiments, the corrosion inhibitor can be a phosphate ester, aderivative of the phosphate ester, a diacid, a derivative of the diacid,a quat amine, a derivative of the quat amine, an imidazoline, aderivative of the imidazoline, an alkyl pyridine, a derivative of thealkyl pyridine, a phosphonium salt, a derivative of the phosphoniumsalt, or a combination thereof.

In an embodiment, the corrosion inhibitors include neutralizing amines.Suitable neutralization amines include morpholine, methoxypropylamine,ethyienediamine, monoethanolalmine, dimethylethanolaminediethylhydroxylamine, and hydrazine didrates.

In an embodiment, the corrosion inhibitors include cationic surfactantcomprising an ammonium halide. The ammonium halide may include anysuitable types of ammonium halides. In embodiments, the ammonium halidesinclude alkyl ammonium halides, polyalkyl ammonium halides, benzyltriethyl ammonium halides or any combinations thereof. In embodiments,the cationic surfactant includes any combination or at least one of analkyl trimethyl ammonium halide, alkyl triethyl ammonium halide, analkyl dimethyl benzyl ammonium halide, and one or more imidazoliniumhalides.

In an embodiment, the corrosion inhibitors include phosphonates,including phosphonic acid and esters, such as tetrahydrothiazolesphosphonic acids or esters. Additional phosphorus-based compounds may besuitable for use, including thiophosphonic acid and the salts and alkyl,and aryl esters of the same.

In an aspect of the invention, a corrosion inhibitor is present in a usesolution in an amount between about 1 ppm to 50,000 ppm. In a furtheraspect, a corrosion inhibitor is present in a use solution in an amountof at least about 0.0001 wt-% to about 10 wt-%, preferably at leastabout 0.0001 wt-% to about 5 wt-%, preferably at least about 0.0001 wt-%to about 1 wt-%, preferably at least about 0.0001 wt-% to about 0.1wt-%, and still more preferably at least about 0.0001 wt-% to about 0.05wt-%.

Beneficially, the compositions and methods of the invention do notnegatively interfere with corrosion inhibitor included in an aqueoussolution. As a further benefit, the use of the two-part peroxycarboxylicacid forming compositions according to the invention allow formulationof the corrosion inhibitors directly into either of the premixformulations, overcoming a substantial limitation of the prior artwherein conventional corrosion inhibitors are not sufficiently stable inother equilibrium chemistries. The two-part premixes according toembodiments of the invention allow formulation of the corrosioninhibitors directly into a premix and thereby reducing the number ofinputs required for a system to be treated according to the methods andchemistries of the present invention.

Scale Inhibitors

Scale inhibitors are additional molecules used in oil and gas recoveryoperations. Common scale inhibitors that may be employed in these typesof applications include polymers and co-polymers, phosphates, phosphateesters and the like.

In an aspect of the invention, a scale inhibitor is present in a usesolution in an amount between about 1 ppm to about 5,000 ppm, or fromabout 100 ppm to 5,000 ppm. In a further aspect, a scale inhibitor ispresent in a use solution in an amount of at least about 0.0001 wt-% toabout 10 wt-%, at least about 0.0001 wt-% to about 1 wt-%, preferably atleast about 0.0001 wt-% to about 0.1 wt-%, preferably at least about0.0001 wt-% to about 0.05 wt-%. Beneficially, the compositions andmethods of the invention do not negatively interfere with scaleinhibitor included in an aqueous solution.

Additional Antimicrobial Agents

Additional antimicrobial agents may be included in the compositionsand/or methods of the invention for enhanced antimicrobial efficacy. Inaddition to the use of peracid compositions, additional antimicrobialagents and biocides may be employed. Additional biocides may include,for example, a quaternary ammonium compound as disclosed in U.S. Pat.No. 6,627,657, which is incorporated herein by reference in itsentirety. Beneficially, the presence of the quaternary ammonium compoundprovides both synergistic antimicrobial efficacies with peracids, aswell as maintains long term biocidal efficacy of the compositions.

In another embodiment, the additional biocide may include an oxidizercompatible phosphonium biocide, such as tributyl tetradecyl phosphoniumchloride. The phosphonium biocide provides similar antimicrobialadvantages as the quaternary ammonium compound in combination with theperacids. In addition, the phosphonium biocide is compatible with theanionic polymeric chemicals commonly used in the oil field applications,such as the methods of the fracking disclosed according to theinvention.

Additional antimicrobial and biocide agents may be employed in amountssufficient to provide antimicrobial efficacy, as may vary depending uponthe water source in need of treatment and the contaminants therein. Suchagents may be present in a use solution in an amount of at least about0.1 wt-% to about 5 wt-%, preferably at least about 0.1 wt-% to about 2wt-%, more preferably from about 0.1 wt-% to about 1 wt-%.

Acidulants

Acidulants may be included as additional functional ingredients in acomposition according to the invention. In an aspect, a strong mineralacid such as nitric acid or sulfuric acid can be used to treat watersources, as disclosed in U.S. Pat. No. 4,587,264, which is incorporatedherein by reference in its entirety. The combined use of a strongmineral acid with the peracid composition provides enhancedantimicrobial efficacy as a result of the acidity assisting in removingchemical contaminants within the water source (e.g. sulfite and sulfidespecies). In addition, some strong mineral acids, such as nitric acid,provide a further benefit of reducing the risk of corrosion towardmetals contacted by the peracid compositions according to the invention.In some embodiments, the present composition does not comprise a mineralacid or a strong mineral acid.

In an aspect, the acidulant is included in the second reagent withhydrogen peroxide. Any suitable acid can be included in the compositionsas an acidulant. In an embodiment the acidulant is an acid or an aqueousacidic solution. In an embodiment, the acidulant includes an inorganicacid. In some embodiments, the acidulant is a strong mineral acid.Suitable inorganic acids include, but are not limited to, sulfuric acid,sodium bisulfate, phosphoric acid, nitric acid, hydrochloric acid. Insome embodiments, the acidulant includes an organic acid. Suitableorganic acids include, but are not limited to, methane sulfonic acid,ethane sulfonic acid, propane sulfonic acid, butane sulfonic acid,xylene sulfonic acid, cumene sulfonic acid, benzene sulfonic acid,formic acid, acetic acid, mono, di, or tri-halocarboyxlic acids,picolinic acid, dipicolinic acid, and mixtures thereof.

Acidulants may be employed in amounts sufficient to provide the intendedantimicrobial efficacy and/or anticorrosion benefits, as may varydepending upon the water source or surface in need of treatment and thecontaminants therein. Such agents may be present in a use solution in anamount of at least about 0.1 wt-% to about 10 wt-%, preferably at leastabout 0.1 wt-% to about 5 wt-%, more preferably from about 0.1 wt-% toabout 1 wt-%.

Catalase and Peroxidase Enzyme

In an aspect of the invention, a catalase or peroxidase enzyme can beused to reduce and/or eliminate the concentration of hydrogen peroxidein an antimicrobial peracid composition. The enzymes catalyze thedecomposition of hydrogen peroxide to water and oxygen.

Various sources of catalase enzymes may be employed according to theinvention, including: animal sources such as bovine catalase isolatedfrom beef livers; fungal catalases isolated from fungi includingPenicillium chrysogenum, Penicillium notatum, and Aspergillus niger;plant sources; bacterial sources such as Staphylcoccus aureus, andgenetic variations and modifications thereof. In an aspect of theinvention, fungal catalases are utilized to reduce the hydrogen peroxidecontent of a peracid composition. Catalases are commercially availablein various forms, including liquid and spray dried forms. Commerciallyavailable catalase includes both the active enzyme as well as additionalingredients to enhance the stability of the enzyme. Some exemplarycommercially available catalase enzymes include Genencor CA-100 andCA-400, as well as Mitsubishi Gas and Chemical (MGC) ASC super G and ASCsuper 200, and Optimase CA 400L from Genecor International. Additionaldescription of suitable catalase enzymes are disclosed and hereinincorporated by reference in its entirety from U.S. Patent PublicationNo. 2009/0269324.

In an aspect of the invention, catalase enzymes have a high ability todecompose hydrogen peroxide. Beneficially, the reduction or eliminationof hydrogen peroxide from oxidizing compositions obviates the variousdetriments caused by oxidizing agents. In particular, the use ofcatalase with the peracids compositions provides enhanced antimicrobialbenefits without causing the damage associated with conventionaloxidizing agents (e.g. peracetic acid, hypochlorite or hypochlorousacid, and/or chlorine dioxide), such as corrosion.

Peroxidase enzymes may also be employed to decompose hydrogen peroxidefrom a peracid composition. Although peroxidase enzymes primarilyfunction to enable oxidation of substrates by hydrogen peroxide, theyare also suitable for effectively lowering hydrogen peroxide to peracidratios in compositions. Various sources of peroxidase enzymes may beemployed according to the invention, including for example animalsources, fungal peroxidases, and genetic variations and modificationsthereof. Peroxidases are commercially available in various forms,including liquid and spray dried forms. Commercially availableperoxidases include both the active enzyme as well as additionalingredients to enhance the stability of the enzyme.

In some embodiments, the catalase or peroxidase enzyme is able todegrade at least about 50% of the initial concentration of hydrogenperoxide in a peracid composition. Preferably, the enzyme is provided insufficient amount to reduce the hydrogen peroxide concentration of aperacid composition by at least more than about 50%, more preferably atleast about 60%, at least about 70%, at least about 80%, at least about90%. In some embodiments, the enzyme reduces the hydrogen peroxideconcentration of a peracid composition by more than 90%.

In an aspect of the invention, the enzymes are suitable for use and havea tolerance to a wide range of temperatures, including the temperaturesranges in water treatment applications which may range from about 0-80C. A suitable catalase enzyme will maintain at least 50% of its activityunder such storage and/or application temperatures for at least about 10minutes, preferably for at least about 1 hour.

In an aspect of the invention, a catalase or peroxidase enzyme ispresent in a use solution of the peracid composition in sufficientamounts to reduce the concentration of hydrogen peroxide from theperacid composition by at least 50% within about 10 minutes, preferablywithin about 5 minutes, preferably within about 2 to 5 minutes, morepreferably within about 1 minute. The ranges of concentration of theenzymes will vary depending upon the amount of time within which 50% ofthe hydrogen peroxide from the peracid composition is removed. Incertain aspects of the invention, a catalase or peroxidase enzyme ispresent in a use solution composition including the water source to betreated in amounts between about 1 ppm and about 1,000 ppm, preferablybetween about 5 ppm and 500 ppm, and more preferably between about 10ppm and about 100 ppm.

Wetting Agents

In an aspect, a wetting agent is present in a use solution of theperacid composition in sufficient amounts. Wetting agents function toincrease the surface contact or penetration activity of the peroformicacid composition of the invention. Wetting agents which can be used inthe composition of the invention include any of those constituents knownwithin the art to raise the surface activity of the composition of theinvention. In an exemplary aspect, the wetting agent is a sulfonic acidor salt thereof (e.g., dodecylbenzene sulfonic acid, sodium salt). Incertain embodiments, the wetting agent is present in amounts from about0.001 to about 10 wt-% wetting agent, about 0.01 to about 1 wt-% wettingagent, about 0.01 to about 0.5 wt-% wetting agent, or about 0.1 to about0.5 wt-% wetting agent.

Stabilizing Agents

In an aspect, the peroxyformic acid compositions can further comprise astabilizing agent for the peroxyformic acid and/or a stabilizing agentfor hydrogen peroxide. In an aspect, the peroxyformic acid formingcompositions can further comprise peroxide, and/or a pH buffering agent.The present peroxyformic acid forming compositions can comprise anysuitable pH buffering agent stabilizing agent. Exemplary stabilizingagents include a phosphonate salt(s) and/or a heterocyclic dicarboxylicacid, e.g., dipicolinic acid. In some embodiments, the stabilizing agentis pyridine carboxylic acid based stabilizers, such as picolinic acidand salts, pyridine-2,6-dicarboxylic acid and salts, and phosphonatebased stabilizers, such as phosphoric acid and salts, pyrophosphoricacid and salts and most commonly 1-hydroxyethylidene-1,1-diphosphonicacid (HEDP) and salts. In other embodiments, the presentperoxycarboxylic acid forming compositions comprise two or morestabilizing agents, e.g., HEDP and 2,6-pyridinedicarboxylic acid (DPA).In an aspect the stabilizing agent(s) can be comprised in any suitablepart of the present peroxyformic acid forming compositions. In someembodiments, the first reagent comprises a stabilizing agent for theperoxyformic acid and/or a pH buffering agent. In other embodiments, thesecond reagent comprises a stabilizing agent for hydrogen peroxide. Instill other embodiments, the present peroxyformic acid formingcompositions can further comprise a third reagent that comprises astabilizing agent for the peroxyformic acid, a stabilizing agent forhydrogen peroxide, and/or a pH buffering agent. In yet otherembodiments, the solid composition comprises a stabilizing agent forperoxyformic acid, a stabilizing agent for hydrogen peroxide, and/or apH buffering agent.

In an aspect, the peroxyformic acid forming compositions can furthercomprise any suitable pH buffering agent. The pH buffer reagent caninclude any reagent that is compatible with the ester(s) in theperoxyformic acid forming compositions. Exemplary buffer agents suitablefor using with a liquid ester can be an organic amine, such astriethanol amine, imidazole, etc. Exemplary buffer agents suitable forusing with a solid form of ester include a broader range of buffers,such as a carbonate salt, a phosphate salt, etc. The pH buffer reagentcan be comprised in any suitable part of the present peroxyformic acidforming compositions. In some embodiments, the first reagent comprises apH buffering agent. In other embodiments, the peroxyformic acid formingcompositions can further comprise a third reagent that comprises a pHbuffering agent. In still other embodiments, the solid compositioncomprises a pH buffering agent.

In an aspect, the peroxyformic acid forming compositions can furthercomprise any suitable stabilizing agent for hydrogen peroxide. Exemplarystabilizing agents for hydrogen peroxide include phosphonates,heterocyclic carboxylic acids and the mixtures thereof. In someembodiments, stabilizing agents for hydrogen peroxide can be Dequest2010, Dequest 2066, Dipicolinic acids, etc. The stabilizing agent forhydrogen peroxide can be comprised in any suitable part of theperoxyformic acid forming compositions. In some embodiments, the secondreagent comprises a stabilizing agent for hydrogen peroxide. In otherembodiments, the peroxyformic acid forming compositions can furthercomprise a third reagent that comprises a stabilizing agent for hydrogenperoxide. In still other embodiments, the solid composition comprises astabilizing agent for hydrogen peroxide.

Alkalinity Source

The peroxyformic acid forming compositions may require pH adjustmentwith an alkalinity source. In an exemplary aspect, in the event areagent of the self-indicating peracid chemistry includes an acidiccomponent, such as a wetting agent, an alkalinity source may bedesirable to increase the strongly acidic pH to ensure the perhydrolysisreaction to generate the peroxyformic acid is not slowed.

Suitable sources of alkalinity can include, but is not limited to, analkaline metal hydroxide, an alkaline earth metal hydroxide, an alkalimetal silicate, an alkali metal carbonate, borates, amines, amides orother basic nitrogen sources and mixtures thereof. Suitable alkalinemetal hydroxides include, but are not limited to, sodium hydroxide,potassium hydroxide and mixtures thereof. Suitable alkaline earth metalhydroxides include, but are not limited to, magnesium hydroxide, calciumhydroxide and mixtures and derivatives thereof. Suitable alkali metalsilicates include but are not limited to, sodium silicate andderivatives thereof. Suitable amines include, but are not limited to,primary, secondary or tertiary amines and diamines carrying at least onenitrogen linked hydrocarbon group, which represents a saturated orunsaturated linear or branched alkyl group having at least 1 carbonatom. Amines may further include alkanolamines including, for example,monoethanolamine, monoisopropanolamine, diethanolamine,diisopropanolamine, triethanolamine, triisopropanolamine and the like.

Surfactants

In some aspects of the invention, the peroxyformic acid compositions orone of the reagents employed in forming the peroxyformic acid include atleast one surfactant. Surfactants are preferably included to increasesolubility of the peroxyformic acid or to maintain the pH of thecomposition. According to an embodiment of the invention, the surfactantis a hydrotrope coupler or solubilizer, which can be used to ensure thatthe composition remains phase stable and in a single highly activeaqueous form. Such hydrotrope solubilizers or couplers can be used atconcentrations that maintain phase stability but do not result inunwanted compositional interaction. Surfactants particularly suitablefor use with the compositions of the present invention include, but arenot limited to, nonionic surfactants, anionic surfactants, amphotericsurfactants and zwitterionic surfactants. Preferably, nonionic and/oranionic surfactants are employed with the peracid compositions of theinvention. Exemplary surfactants that can be used are commerciallyavailable from a number of sources. For a discussion of surfactants, seeKirk-Othmer, Encyclopedia of Chemical Technology, Third Edition, volume8, pages 900-912.

Peracids are known to be strong oxidation agents, and as a result manychemicals, including commonly used surfactants are not compatible withconcentrated peracids for extended presence of peracids. While it isideal to use surfactants along with peracids to deliver preferredperformance, such as cleaning, wetting et al., there is very limitedchoice of surfactants that could be put in preformed peracidformulations that meet the minimum shelf life requirements forcommercial use. For examples, nonionic surfactants will be degraded byperacids, and cationic surfactants with halogen counter anions willdecompose peracids. Some anionic surfactants, namely non substitutedalkyl sulfonates, such as linear alkylbenzensulfonate (LAS), lineralkylsulfonate are more compatible with peracids and maybe used in someperacids compositions, but these anionic surfactants may not deliver thedesired performance owing to their unwanted properties, such as highfoam, water hardness tolerance as well as regulation requirements. Incontrast, for onsite generated peracid compositions such as disclosed inthe present art, all surfactants described above could be coexist withthe peracids, as the generated peracids are only stored for very limitedtime, and typically in hours at the most, and the reactions between thesurfactants and the peracids are not significant.

According to a preferred embodiment of the invention, the surfactant isan acidic anionic surfactant. According to a further embodiment, thesurfactant is an antimicrobial agent. Exemplary surfactant, hydrotropesolubilizers include anionic surfactants such as an alkyl sulfate, anaryl sulfonate, an alkyl or alkane sulfonate, a linear alkyl benzene ornaphthalene sulfonate, a secondary alkane sulfonate, alkyl ether sulfateor sulfonate, an alkyl phosphate or phosphonate, dialkyl sulfosuccinicacid ester, sugar esters (e.g., sorbitan esters) and a C₈₋₁₀ alkylglucoside.

In some embodiments, the compositions of the present invention includesfrom about 1 wt-% to about 80 wt-% of a surfactant. In other embodimentsthe compositions of the present invention include from about 1 wt-% toabout 50 wt-% of a surfactant. In additional embodiments, thecompositions of the present invention include from about 1 wt-% to about10 wt-% of a surfactant. In further embodiments, the compositions of thepresent invention or a use solution of the peroxyformic acid compositioninclude about 10 ppm to about 10,000 ppm of a surfactant. In furtherembodiments, the compositions of the present invention or a use solutionof the peroxyformic acid composition include about 10 ppm to about 100ppm of a surfactant. It is to be understood that all ranges and valuesbetween these ranges and values are encompassed by the presentinvention.

Nonionic Surfactants

Suitable nonionic surfactants suitable for use with the compositions ofthe present invention include alkoxylated surfactants. Suitablealkoxylated surfactants include EO/PO copolymers, capped EO/POcopolymers, alcohol alkoxylates, capped alcohol alkoxylates, mixturesthereof, or the like. Suitable alkoxylated surfactants for use assolvents include EO/PO block copolymers, such as the Pluronic andreverse Pluronic surfactants; alcohol alkoxylates; and capped alcoholalkoxylates, such as Plurafac LF221; mixtures thereof, or the like.

Semi-Polar Nonionic Surfactants

The semi-polar type of nonionic surface active agents are another classof nonionic surfactant useful in compositions of the present invention.Semi-polar nonionic surfactants include the amine oxides, phosphineoxides, sulfoxides and their alkoxylated derivatives.

Amine oxides are tertiary amine oxides corresponding to the generalformula:

wherein the arrow is a conventional representation of a semi-polar bond;and, R¹, R², and R³ may be aliphatic, aromatic, heterocyclic, alicyclic,or combinations thereof. Generally, for amine oxides of detergentinterest, R¹ is an alkyl radical of from about 8 to about 24 carbonatoms; R² and R³ are alkyl or hydroxyalkyl of 1-3 carbon atoms or amixture thereof; R² and R³ can be attached to each other, e.g. throughan oxygen or nitrogen atom, to form a ring structure; R⁴ is an alkyleneor a hydroxyalkylene group containing 2 to 3 carbon atoms; and n rangesfrom 0 to about 20. An amine oxide can be generated from thecorresponding amine and an oxidizing agent, such as hydrogen peroxide.

Useful water soluble amine oxide surfactants are selected from theoctyl, decyl, dodecyl, isododecyl, coconut, or tallow alkyl di-(loweralkyl)amine oxides, specific examples of which are octyldimethylamineoxide, nonyldimethylamine oxide, decyldimethylamine oxide,undecyldimethylamine oxide, dodecyldimethylamine oxide,iso-dodecyldimethyl amine oxide, tridecyldimethylamine oxide,tetradecyldimethylamine oxide, pentadecyldimethylamine oxide,hexadecyldimethylamine oxide, heptadecyldimethylamine oxide,octadecyldimethylaine oxide, dodecyldipropylamine oxide,tetradecyldipropylamine oxide, hexadecyldipropylamine oxide,tetradecyldibutylamine oxide, octadecyldibutylamine oxide,bis(2-hydroxyethyl)dodecylamine oxide,bis(2-hydroxyethyl)-3-dodecoxy-1-hydroxypropylamine oxide,dimethyl-(2-hydroxydodecyl)amine oxide, 3,6,9-trioctadecyldimethylamineoxide and 3-dodecoxy-2-hydroxypropyldi-(2-hydroxyethyl)amine oxide.

Anionic Surfactants

Anionic sulfate surfactants suitable for use in the present compositionsinclude alkyl ether sulfates, alkyl sulfates, the linear and branchedprimary and secondary alkyl sulfates, alkyl ethoxysulfates, fatty oleylglycerol sulfates, alkyl phenol ethylene oxide ether sulfates, theC₅-C₁₇ acyl-N—(C₁-C₄ alkyl) and —N—(C₁-C₂ hydroxyalkyl)glucaminesulfates, and sulfates of alkylpolysaccharides such as the sulfates ofalkylpolyglucoside, and the like. Also included are the alkyl sulfates,alkyl poly(ethyleneoxy)ether sulfates and aromaticpoly(ethyleneoxy)sulfates such as the sulfates or condensation productsof ethylene oxide and nonyl phenol (usually having 1 to 6 oxyethylenegroups per molecule).

Anionic sulfonate surfactants suitable for use in the presentcompositions also include alkyl sulfonates, the linear and branchedprimary and secondary alkyl sulfonates, and the aromatic sulfonates withor without substituents.

Anionic carboxylate surfactants suitable for use in the presentcompositions include carboxylic acids (and salts), such as alkanoicacids (and alkanoates), ester carboxylic acids (e.g. alkyl succinates),ether carboxylic acids, and the like. Such carboxylates include alkylethoxy carboxylates, alkyl aryl ethoxy carboxylates, alkyl polyethoxypolycarboxylate surfactants and soaps (e.g. alkyl carboxyls). Secondarycarboxylates useful in the present compositions include those whichcontain a carboxyl unit connected to a secondary carbon. The secondarycarbon can be in a ring structure, e.g. as in p-octyl benzoic acid, oras in alkyl-substituted cyclohexyl carboxylates. The secondarycarboxylate surfactants typically contain no ether linkages, no esterlinkages and no hydroxyl groups. Further, they typically lack nitrogenatoms in the head-group (amphiphilic portion). Suitable secondary soapsurfactants typically contain 11-13 total carbon atoms, although morecarbons atoms (e.g., up to 16) can be present. Suitable carboxylatesalso include acylamino acids (and salts), such as acylgluamates, acylpeptides, sarcosinates (e.g. N-acyl sarcosinates), taurates (e.g. N-acyltaurates and fatty acid amides of methyl tauride), and the like.

Suitable anionic surfactants include alkyl or alkylaryl ethoxycarboxylates of the following formula: R—O—(CH₂CH₂O)_(n)(CH₂)_(m)—CO₂Xin which R is a C₈ to C₂₂ alkyl group or

in which R₁ is a C₄-C₁₆ alkyl group; n is an integer of 1-20; m is aninteger of 1-3; and X is a counter ion, such as hydrogen, sodium,potassium, lithium, ammonium, or an amine salt such as monoethanolamine,diethanolamine or triethanolamine. In some embodiments, n is an integerof 4 to 10 and m is 1. In some embodiments, R is a C₈-C₁₆ alkyl group.In some embodiments, R is a C₁₂-C₁₄ alkyl group, n is 4, and m is 1.

In other embodiments, R is

and R₁ is a C₆-C₁₂ alkyl group. In still yet other embodiments, R₁ is aC₉ alkyl group, n is 10 and m is 1.

Such alkyl and alkylaryl ethoxy carboxylates are commercially available.These ethoxy carboxylates are typically available as the acid forms,which can be readily converted to the anionic or salt form.

Amphoteric Surfactants

Amphoteric, or ampholytic, surfactants contain both a basic and anacidic hydrophilic group and an organic hydrophobic group. These ionicentities may be any of anionic or cationic groups described herein forother types of surfactants. A basic nitrogen and an acidic carboxylategroup are the typical functional groups employed as the basic and acidichydrophilic groups. In a few surfactants, sulfonate, sulfate,phosphonate or phosphate provide the negative charge.

Amphoteric surfactants can be broadly described as derivatives ofaliphatic secondary and tertiary amines, in which the aliphatic radicalmay be straight chain or branched and wherein one of the aliphaticsubstituents contains from about 8 to 18 carbon atoms and one containsan anionic water solubilizing group, e.g., carboxy, sulfo, sulfato,phosphate, or phosphono. Amphoteric surfactants are subdivided into twomajor classes known to those of skill in the art and described in“Surfactant Encyclopedia” Cosmetics & Toiletries, Vol. 104 (2) 69-71(1989), which is herein incorporated by reference in its entirety. Thefirst class includes acyl/dialkyl ethylenediamine derivatives (e.g.2-alkyl hydroxyethyl imidazoline derivatives) and their salts. Thesecond class includes N-alkylamino acids and their salts. Someamphoteric surfactants can be envisioned as fitting into both classes.

Amphoteric surfactants can be synthesized by methods known to those ofskill in the art. For example, 2-alkyl hydroxyethyl imidazoline issynthesized by condensation and ring closure of a long chain carboxylicacid (or a derivative) with dialkyl ethylenediamine. Commercialamphoteric surfactants are derivatized by subsequent hydrolysis andring-opening of the imidazoline ring by alkylation—for example withchloroacetic acid or ethyl acetate. During alkylation, one or twocarboxy-alkyl groups react to form a tertiary amine and an ether linkagewith differing alkylating agents yielding different tertiary amines.

Exemplary suitable amphoteric surfactants include long chain imidazolederivatives, including carboxymethylated compounds (glycinates) whichare frequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants. These and other amphoteric surfactants are furtherdescribed in U.S. patent application Ser. No. 12/568,493, entitled“Sulfoperoxycarboxylic Acids, Their Preparation and Methods of Use asBleaching and Antimicrobial Agents,” hereby expressly incorporatedherein in its entirety by reference.

Long chain imidazole derivatives having application in the presentinvention generally have the general formula:

wherein R is an acyclic hydrophobic group containing from about 8 to 18carbon atoms and M is a cation to neutralize the charge of the anion,generally sodium. Commercially prominent imidazoline-derived amphotericsthat can be employed in the present compositions include for example:Cocoamphopropionate, Cocoamphocarboxy-propionate, Cocoamphoglycinate,Cocoamphocarboxy-glycinate, Cocoamphopropyl-sulfonate, andCocoamphocarboxy-propionic acid. Amphocarboxylic acids can be producedfrom fatty imidazolines in which the dicarboxylic acid functionality ofthe amphodicarboxylic acid is diacetic acid and/or dipropionic acid.

The carboxymethylated compounds (glycinates) described herein abovefrequently are called betaines. Betaines are a special class ofamphoteric discussed herein below in the section entitled, ZwitterionSurfactants.

Additionally suitable amphoteric surfactants include long chainN-alkylamino acids which are readily prepared by reaction RNH₂, in whichR═C₈-C₁₈ straight or branched chain alkyl, fatty amines with halogenatedcarboxylic acids. Alkylation of the primary amino groups of an aminoacid leads to secondary and tertiary amines. Alkyl substituents may haveadditional amino groups that provide more than one reactive nitrogencenter. Most commercial N-alkylamine acids are alkyl derivatives ofbeta-alanine or beta-N(2-carboxyethyl)alanine. Examples of commercialN-alkylamino acid ampholytes having application in this inventioninclude alkyl beta-amino dipropionates, RN(C₂H₄COOM)₂ and RNHC₂H₄COOM.In an embodiment, R can be an acyclic hydrophobic group containing fromabout 8 to about 18 carbon atoms, and M is a cation to neutralize thecharge of the anion.

Suitable amphoteric surfactants include those derived from coconutproducts such as coconut oil or coconut fatty acid. Additional suitablecoconut derived surfactants include as part of their structure anethylenediamine moiety, an alkanolamide moiety, an amino acid moiety,e.g., glycine, or a combination thereof; and an aliphatic substituent offrom about 8 to 18 (e.g., 12) carbon atoms. Such a surfactant can alsobe considered an alkyl amphodicarboxylic acid. These amphotericsurfactants can include chemical structures represented as:C₁₂-alkyl-C(O)—NH—CH₂—CH₂—N⁺(CH₂—CH₂—CO₂Na)₂—CH₂—CH₂—OH orC₁₂-alkyl-C(O)—N(H)—CH₂—CH₂—N⁺(CH₂—CO₂Na)₂—CH₂—CH₂—OH. Disodiumcocoampho dipropionate is one suitable amphoteric surfactant and iscommercially available under the tradename Miranol™ FBS from Rhodia Inc.(Cranbury, N.J.). Another suitable coconut derived amphoteric surfactantwith the chemical name disodium cocoampho diacetate is sold under thetradename Mirataine™ JCHA, also from Rhodia Inc.

A typical listing of amphoteric classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975 and further examples are given in “SurfaceActive Agents and Detergents” (Vol. I and II by Schwartz, Perry andBerch), each of which are hereby expressly incorporated herein in itsentirety by reference.

Zwitterionic Surfactants

Zwitterionic surfactants can be thought of as a subset of the amphotericsurfactants and can include an anionic charge. Zwitterionic surfactantscan be broadly described as derivatives of secondary and tertiaryamines, derivatives of heterocyclic secondary and tertiary amines, orderivatives of quaternary ammonium, quaternary phosphonium or tertiarysulfonium compounds. Typically, a zwitterionic surfactant includes apositive charged quaternary ammonium or, in some cases, a sulfonium orphosphonium ion; a negative charged carboxyl group; and an alkyl group.Zwitterionics generally contain cationic and anionic groups which ionizeto a nearly equal degree in the isoelectric region of the molecule andwhich can develop strong “inner-salt” attraction betweenpositive-negative charge centers. Examples of such zwitterionicsynthetic surfactants include derivatives of aliphatic quaternaryammonium, phosphonium, and sulfonium compounds, in which the aliphaticradicals can be straight chain or branched, and wherein one of thealiphatic substituents contains from 8 to 18 carbon atoms and onecontains an anionic water solubilizing group, e.g., carboxy, sulfonate,sulfate, phosphate, or phosphonate. Betaine and sultaine surfactants areexemplary zwitterionic surfactants for use herein.

A general formula for these compounds is:

wherein R¹ contains an alkyl, alkenyl, or hydroxyalkyl radical of from 8to 18 carbon atoms having from 0 to 10 ethylene oxide moieties and from0 to 1 glyceryl moiety; Y is selected from the group consisting ofnitrogen, phosphorus, and sulfur atoms; R² is an alkyl or monohydroxyalkyl group containing 1 to 3 carbon atoms; x is 1 when Y is a sulfuratom and 2 when Y is a nitrogen or phosphorus atom, R³ is an alkylene orhydroxy alkylene or hydroxy alkylene of from 1 to 4 carbon atoms and Zis a radical selected from the group consisting of carboxylate,sulfonate, sulfate, phosphonate, and phosphate groups.

Examples of zwitterionic surfactants having the structures listed aboveinclude:4-[N,N-di(2-hydroxyethyl)-N-octadecylammonio]-butane-1-carboxylate;5-[S-3-hydroxypropyl-S-hexadecylsulfonio]-hydroxypentane-1-sulfate;3-[P,P-diethyl-P-3,6,9-trioxatetracosanephosphonio]-2-hydroxypropane-1-phosphate;3-[N,N-dipropyl-N-3dodecoxy-2-hydroxypropyl-ammonio]-propane-1-phosphonate;3-(N,N-dimethyl-N-hexadecylammonio)-propane-1-sulfonate;3-(N,N-dimethyl-N-hexadecylammonio)-2-hydroxy-propane-1-sulfonate;4-[N,N-di(2(2-hydroxyethyl)-N(2-hydroxydodecyl)ammonio]-butane-1-carboxylate;3-[S-ethyl-S-(3-dodecoxy-2-hydroxypropyl)sulfonio]-propane-1-phosphate;3-[P,P-dimethyl-P-dodecylphosphonio]-propane-1-phosphonate; and S[N,N-di(3-hydroxypropyl)-N-hexadecylammonio]-2-hydroxy-pentane-1-sulfate.The alkyl groups contained in said detergent surfactants can be straightor branched and saturated or unsaturated.

The zwitterionic surfactant suitable for use in the present compositionsincludes a betaine of the general structure:

These surfactant betaines typically do not exhibit strong cationic oranionic characters at pH extremes nor do they show reduced watersolubility in their isoelectric range. Unlike “external” quaternaryammonium salts, betaines are compatible with anionics. Examples ofsuitable betaines include coconut acylamidopropyldimethyl betaine;hexadecyl dimethyl betaine; C₁₂₋₁₄ acylamidopropylbetaine; C₈₋₁₄acylamidohexyldiethyl betaine; 4-C₁₄₋₁₆acylmethylamidodiethylammonio-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; andC₁₂₋₁₆ acylmethylamidodimethylbetaine.

Sultaines useful in the present invention include those compounds havingthe formula (R(R¹)₂N⁺R²SO³⁻, in which R is a C₆-C₁₈ hydrocarbyl group,each R¹ is typically a C₁-C₃ alkyl, e.g. methyl, and R² is a C₁-C₆hydrocarbyl group, e.g. a C₁-C₃ alkylene or hydroxyalkylene group.

A typical listing of zwitterionic classes, and species of thesesurfactants, is given in U.S. Pat. No. 3,929,678 issued to Laughlin andHeuring on Dec. 30, 1975. Further examples are given in “Surface ActiveAgents and Detergents” (Vol. I and II by Schwartz, Perry and Berch).Each of these references are herein incorporated in their entirety.

Self-Indicating Chemistries

In an aspect, various self-indicating chemistries are suitable for usewith the peroxyformic acid chemistries according to the invention. In anaspect, the self-indicating chemistry compositions comprise acombination of at least two dyes. In a further aspect, theself-indicating chemistry compositions comprise a combination of threedyes. In a further aspect, the combination of dyes provides a visualindication system suitable for detecting the formation or generation ofa peroxycarboxylic acid formed in a perhydrolysis reaction. Preferably,the combination of dyes provides a visual indication system using threedistinct colors (e.g. blue, green, yellow). In an aspect, thecombination of dyes provides a non-fluorescent visual indicator for theperoxycarboxylic acid compositions.

Suitable dyes for use in the self-indicating chemistry compositioninclude oxidize able dyes, including those insensitive to hydrogenperoxide driving a perhydrolysis reaction to generation aperoxycarboxylic acid composition. In an aspect, the self-indicatingchemistry composition include a combination of dyes having differenthalf-lives in order to provide sustained visual indicators, such as forup to 7 days, or from 1 to 7 days, or from 12 hours to 7 days. In anaspect, the self-indicating chemistry composition include a combinationof HRP substrates and synthetic dyes. Suitable chemistries are disclosedin U.S. Ser. No. 62/216,435, which is herein incorporated by referencein its entirety.

Methods for Treating a Target

In still another aspect, the present invention is directed to a methodfor treating a surface or a target, which method comprises contacting asurface or a target with an effective amount of peroxyformic acid formedusing the above methods to form a treated surface or target composition,wherein said treated surface or target composition comprises from about0.1 ppm to about 10,000 ppm of said peroxyformic acid, and saidcontacting step lasts for sufficient time to stabilize or reducemicrobial population in and/or on said surface or target or said treatedsurface of target composition.

In some embodiments, the composition used in the present methods is anequilibrated composition that comprises peroxyformic acid, hydrogenperoxide, formic acid and a solvent, e.g., water. In some embodiments,the composition used in the present methods does not comprise a mineralacid, e.g., the mineral acids disclosed in WO 91/07375.

The peroxyformic acid and the surface or target can be contacted to forma treated target composition comprising any suitable concentration ofsaid peroxyformic acid, e.g., about 0.1-1 ppm, 1-10 ppm, 10-20 ppm,20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm, 250-300 ppm,300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550 ppm, 550-600ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm, 800-850 ppm,850-900 ppm, 900-950 ppm, 950-1,000 ppm, 1,000-1,500 ppm, 1,500-2,000ppm, 2,000-2,500 ppm, 2,500-3,000 ppm, 3,000-3,500 ppm, 3,500-4,000 ppm,4,000-4,500 ppm, or 4,500-5,000 ppm, 5,000-5,500 ppm, 5,500-6,000 ppm,6,000-6,500 ppm, 6,500-7,000 ppm, 7,000-7,500 ppm, 7,500-8,000,8,000-8,500 ppm, 8,500-9,000 ppm, 9,000-9,500 ppm, or 9,500-10,000 ppmof peroxyformic acid.

The composition used in the present methods can retain any suitableconcentration or percentage of the peroxyformic acid activity for anysuitable time after the treated surface or target composition is formed.In some embodiments, the present composition retains at least about 50%,55%, 60%, 65%, 70%, 75%, 80%, 85% or 90% of the initial peroxyformicacid activity for any suitable time after the treated surface or targetcomposition is formed. In other embodiments, the present compositionretains at least about 60% of the initial peroxyformic acid activity forat least 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30minutes, 1, 2, 5, 10, 15, 20 or 24 hours, or longer after the treatedtarget composition is formed.

In some embodiments, the target to be treated by the present methods canbe a food item or a plant item and/or at least a portion of a medium, acontainer, an equipment, a system or a facility for growing, holding,processing, packaging, storing, transporting, preparing, cooking orserving the food item or the plant item. Any suitable concentration ofperoxyformic acid can be used in the present methods. For example, theperoxyformic acid can be used at a concentration from about 1 ppm toabout 100 ppm, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6 ppm,6-7 ppm, 7-8 ppm, 8-9 ppm, 9-10 ppm, 10-15 ppm, 15-20 ppm, 20-25 ppm, or25-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90ppm, 90-100 ppm of peroxyformic acid. In some embodiments, the target isa food item or a plant item and the contacting step minimizes or doesnot induce an organoleptic effect in and/or on the food item or a plantitem.

The present methods can be used for treating any suitable plant item. Insome embodiments, the plant item is a grain, fruit, vegetable or flowerplant item. In other embodiments, the plant item is a living plant itemor a harvested plant item. In still other embodiments, the plant itemcomprises a seed, a tuber, a growing plant, a cutting, or a root stock.In yet other embodiments, the present methods are used for treating aliving plant tissue comprising treating the plant tissue with the abovecomposition in a diluted concentration to stabilize or reduce microbialpopulation in and/or on the plant tissue. In yet other embodiments, thepresent methods are used for growing a plant on a hydroponic substratein a hydroponic liquid supply medium, comprising: (a) establishing agrowing and living plant tissue in the hydroponic substrate; (b)contacting the living plant tissue, the hydroponic substrate and thehydroponic liquid with a composition of the present invention tostabilize or reduce microbial population in and/or on the living planttissue; and (c) harvesting a usable plant product with reduced microbialcontamination.

The present methods can be used for treating any suitable food item. Forexample, the food item can be an animal product, e.g., an animal carcassor an egg, a fruit item, a vegetable item, or a grain item. In someembodiments, the animal carcass can be a beef, pork, veal, buffalo,lamb, fish, sea food or poultry carcass. In other embodiments, the seafood carcass can be scallop, shrimp, crab, octopus, mussel, squid orlobster. In still other embodiments, the fruit item can be a botanicfruit, a culinary fruit, a simple fruit, an aggregate fruit, a multiplefruit, a berry, an accessory fruit or a seedless fruit. In yet otherembodiments, the vegetable item can be a flower bud, a seed, a leaf, aleaf sheath, a bud, a stem, a stem of leaves, a stem shoot, a tuber, awhole-plant sprout, a root or a bulb. In yet other embodiments, thegrain item can be maize, rice, wheat, barley, sorghum, millet, oat,triticale, rye, buckwheat, fonio or quinoa.

In some embodiments, the target to be treated by the present methods canbe a medium, a surface, a container, an equipment, or a system in ahealth care facility, e.g., a physical office or a hospital. Anysuitable concentration of peroxyformic acid can be used in the presentmethods. For example, the peroxyformic acid can be used at aconcentration from about 10 ppm to about 300 ppm, e.g., 10-15 ppm, 15-20ppm, 20-25 ppm, or 25-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250ppm, or 250-300 ppm of peroxyformic acid.

The present methods can be used for treating a target that is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, transporting, preparing,cooking or serving the food item or the plant item. In some embodiments,the target is at least a portion of a container, an equipment, a systemor a facility for holding, processing, packaging, storing, transporting,preparing, cooking or serving a meat item, a fruit item, a vegetableitem, or a grain item. In other embodiments, the target is at least aportion of a container, an equipment, a system or a facility forholding, processing, packaging, storing, or transporting an animalcarcass. In still other embodiments, the target is at least a portion ofa container, an equipment, a system or a facility used in foodprocessing, food service or health care industry. In yet otherembodiments, the target is at least a portion of a fixed in-placeprocess facility. An exemplary fixed in-place process facility cancomprise a milk line dairy, a continuous brewing system, a pumpable foodsystem or a beverage processing line.

The present methods can be used for treating a target that is at least aportion of a solid surface or liquid media. In some embodiments, thesolid surface is an inanimate solid surface. The inanimate solid surfacecan be contaminated by a biological fluid, e.g., a biological fluidcomprising blood, other hazardous body fluid, or a mixture thereof. Inother embodiments, the solid surface can be a contaminated surface. Anexemplary contaminated surface can comprise the surface of food servicewares or equipment, or the surface of a fabric.

The peroxyformic acid can be applied in any suitable manner. In someembodiments, the peroxyformic acid can be applied to a target by meansof a spray, a fog, or a foam, or by dipping all or part of the target ina composition comprising the peroxyformic acid. In some embodiments, theperoxyformic acid composition is applied to the target by means of aspray, a fog, or a foam. In other embodiments, the diluted peroxyformicacid is applied to the target by applying in the form of a thickened orgelled solution. In still other embodiments, all or part of the targetis dipped in the peroxyformic acid composition. The target and/or theperoxyformic acid composition can be subject to any suitable movement tohelp or facilitate the contact between the target and the peroxyformicacid composition. In some embodiments, the peroxyformic acid compositioncan be agitated. In other embodiments, the peroxyformic acid compositioncan be sprayed onto a target, e.g., an animal carcass, under suitablepressure and at a suitable temperature. For example, the peroxyformicacid composition can be sprayed onto an animal carcass at a pressure ofat least 50 psi at a temperature of up to about 60° C., resulting in acontact time of at least 30 seconds.

The present methods can comprise any suitable, additional steps. In someembodiments, the present methods can comprise a vacuum treatment step.In other embodiments, the present methods can comprise a step ofapplying an activated light source to the target, e.g., an animalcarcass.

The contacting step in the present methods can last for any suitableamount of time. In some embodiments, the contacting step can last for atleast about 10 seconds. For example, the contacting step can last for atleast about 10, 20, 30, 40, 50 seconds, 1 minute, 1-2 minutes, 2-3minutes, 3-4 minutes, 4-5 minutes, 5-6 minutes, 6-7 minutes, 7-8minutes, 8-9 minutes, or 9-10 minutes, 10-15 minutes, 15-20 minutes,20-25 minutes, 25-30 minutes, 30-40 minutes, 40-50 minutes, 50-65minutes, 1-2 hours, 2-3 hours, 3-4 hours, 4-5 hours, 5-6 hours, 6-7hours, 7-8 hours, 8-9 hours, or 9-10 hours, 16 hours, 1 day, 3 days, 1week, or longer. In an aspect, the contacting occurs for a period oftime before degradation of the peroxyformic acid composition.

The present methods can be used to reduce microbial population in and/oron the target or the treated target composition by any suitablemagnitude. In some embodiments, the present methods can be used toreduce microbial population in and/or on the target or the treatedtarget composition by at least one log₁₀, two log₁₀, three log₁₀, fourlog₁₀, five log₁₀, or more. In other embodiments, the level of amicroorganism, if present in and/or on the target or the treated targetcomposition, can be stabilized or reduced by the present methods. Forexample, at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90% or moreof the microorganism, if present in and/or on the target or the treatedtarget composition, can be killed, destroyed, removed and/or inactivatedby the present methods.

The present methods can be used to reduce population of any suitablemicrobe(s) in and/or on the target or the treated target composition byany suitable magnitude. In some embodiments, the present methods can beused to reduce a prokaryotic microbial population, e.g., a bacterial oran archaeal population. In other embodiments, the present methods can beused to reduce a eukaryotic microbial population, e.g., a protozoal orfungal population. In still other embodiments, the present methods canbe used to reduce a viral population. Exemplary viral population cancomprise a population of a DNA virus, a RNA virus, and a reversetranscribing virus.

The present methods can be used to stabilize or reduce a microbialpopulation in and/or on the target or the treated target composition,wherein the target is a food item or a plant item and the contactingstep minimizes or does not induce an organoleptic effect in and/or onthe food item or a plant item. Typical organoleptic properties includethe aspects of food or other substances as experienced by the senses,including taste, sight, smell, and touch, in cases where dryness,moisture, and stale-fresh factors are to be considered. See e.g., JasperWomach, the Congressional Research Service document “Report forCongress: Agriculture: A Glossary of Term, Programs, and Laws, 2005Edition.” In some embodiments, organoleptic procedures are performed aspart of the meat and poultry inspections to detect signs of disease orcontamination. In other embodiments, organoleptic tests are conducted todetermine if package materials and components can transfer tastes andodors to the food or pharmaceutical products that they are packaged in.Shelf life studies often use taste, sight, and smell (in addition tofood chemistry and toxicology tests) to determine whether a food productis suitable for consumption. In still other embodiments, organoleptictests are conducted as part of the Hurdle technology. Typically, Hurdletechnology refers to an intelligent combination of hurdles which securesthe microbial safety and stability as well as the organoleptic andnutritional quality and the economic viability of food products. Seegenerally, Leistner L (1995) “In Gould G W (Ed.) New Methods of FoodPreservation, Springer, pp. 1-21; and Leistner I (2000)” InternationalJournal of Food Microbiology, 55:181-186.

The present methods can be conducted at any suitable temperature range.In some embodiments, the present methods can be conducted at atemperature ranging from about 0° C. to about 70° C., e.g., about 0°C.-1° C., 1° C.-2° C., 2° C.-3° C., 3° C.-4° C., 4° C.-5° C., 5° C.-10°C., 10° C.-15° C., 15° C.-20° C., 20° C.-25° C., 25° C.-30° C., 30°C.-35° C., 35° C.-40° C., 40° C.-45° C., 45° C.-50° C., 50° C.-55° C.,55° C.-60° C., 60° C.-65° C., or 65° C.-70° C. In other embodiments, thepresent methods can be conducted at a temperature at or lower than 0° C.

In some embodiments, the present methods can comprise adding aperoxidase or a catalase to further reduce the hydrogen peroxide levelin and/or on the target or the treated target composition. Theperoxidase or catalase can be added in any suitable manner. In someembodiments, the peroxidase or catalase can be added to the target orthe treated target composition before a composition used in the presentmethods is provided to the target. In other embodiments, the presentcompositions can be diluted into a suitable intermediate volume, and theperoxidase or catalase can be added to the diluted, intermediate volume.Thereafter, the diluted, intermediate volume, which contains theperoxidase or catalase, can be added to target. Any suitable peroxidaseor catalase, including the ones described below, can be used in thepresent methods.

Use in Water Treatment

The present methods can be used to treat any suitable surface or target.In some embodiments, the target is water, and the present methods cancomprise providing an effective amount of peroxyformic acid formed usingthe above methods to a water source in need of treatment to form atreated water source, wherein said treated water source comprises fromabout 1 ppm to about 1,000 ppm of said peroxyformic acid, e.g., about1-10 ppm, 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm,500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, 950-1,000 ppm ofperoxyformic acid.

The present methods can be used to treat any suitable water source. Forexample, a water source in need of treatment can be fresh water, pondwater, sea water, produced water, paper manufacturing water, tower wateror a combination thereof.

In some embodiments, the tower water is cooling water and the treatedwater source comprises from about 1 ppm to about 10 ppm of theperoxyformic acid, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6ppm, 6-7 ppm, 7-8 ppm, 8-9 ppm, or 9-10 ppm peroxyformic acid. Thecontacting step can last any suitable amount of time, e.g., about 1-2minutes, 2-3 minutes, 3-4 minutes, 4-5 minutes, 5-6 minutes, 6-7minutes, 7-8 minutes, 8-9 minutes, or 9-10 minutes. The contacting stepcan be conducted at suitable temperature range. For example, thecontacting step can be conducted at a temperature ranging from about 0°C. to about 60° C., e.g., about 0° C.-1° C., 1° C.-2° C., 2° C.-3° C.,3° C.-4° C., 4° C.-5° C., 5° C.-10° C., 10° C.-15° C., 15° C.-20° C.,20° C.-25° C., 25° C.-30° C., 30° C.-35° C., 35° C.-40° C., 40° C.-45°C., 45° C.-50° C., 50° C.-55° C., or 55° C.-60° C.

In some embodiments, the present methods can be used to treat a watersource used in oil or gas drilling operation. For example, the presentmethods can be used to treat a water source used in an operation ofinduced hydraulic fracturing (hydrofracturing or fracking). The watersource can comprise a friction reducer or a viscosity enhancer. Thepresent methods can be used to treat a water source to form a treatedwater source that comprises from about 1 ppm to about 10 ppm of theperoxyformic acid, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6ppm, 6-7 ppm, 7-8 ppm, 8-9 ppm, or 9-10 ppm peroxyformic acid. Thepresent methods can further comprise disposing of the treated watersource. The present methods can further comprise directing the treatedwater source into a subterranean environment, e.g., a subterraneanenvironment that comprises a well in a gas and/or oil. In someembodiments, the target water to be treated contains iron sulfide and/orH2S, and the present methods can be used to oxidize iron sulfide and/orreduce or eliminate H2S in the target water. In other embodiments, thetarget water to be treated needs to be clarified, e.g., containingparticles, and the present methods can be used to clarify the targetwater.

In some embodiments, the target to be treated by the present methods canbe water and/or at least a portion of a medium, a container, anequipment, a system or a facility for producing, holding, processing,packaging, storing, or transporting pulp. The present methods can beused to treat water and/or other target(s) for any suitable purpose. Forexample, the present methods can be used in papermaking, textiles, food,or pharmaceutical industry. The present methods can be used to treat awater source, alone or in combination with other target(s), to form atreated water source that comprises any suitable concentration ofperoxyformic acid, e.g., about 1-2 ppm, 2-3 ppm, 3-4 ppm, 4-5 ppm, 5-6ppm, 6-7 ppm, 7-8 ppm, 8-9 ppm, 9-10 ppm, 10-15 ppm, 15-20 ppm, 20-25ppm, or 25-30 ppm of peroxyformic acid.

The peroxyformic acid compositions can be used for a variety ofindustrial applications, e.g., to reduce microbial or viral populationson a surface or object or in a body or stream of water. In some aspects,the invention includes methods of using the peroxyformic acidcompositions to prevent biological fouling in various industrialprocesses and industries, including oil and gas operations, to controlmicroorganism growth, eliminate microbial contamination, limit orprevent biological fouling in liquid systems, process waters or on thesurfaces of equipment that come in contact with such liquid systems. Asreferred to herein, microbial contamination can occur in variousindustrial liquid systems including, but not limited to, air-bornecontamination, water make-up, process leaks and improperly cleanedequipment. In another aspect, peroxyformic acid and catalasecompositions are used to control the growth of microorganisms in waterused in various oil and gas operations. In a further aspect, thecompositions are suitable for incorporating into fracturing fluids tocontrol or eliminate microorganisms.

As used herein for the methods of the invention, the peroxyformic acidcompositions can employ a variety of peroxyformic acid compositionshaving a low to substantially no hydrogen peroxide concentration. Theseperoxyformic acid compositions include peroxyformic acid compositionswith a catalase or peroxidase enzyme to reduce the hydrogen peroxide toperacid ratio and/or other reduced hydrogen peroxide peroxyformic acidcompositions disclosed herein. In a preferred embodiment peroxyformicacid and catalase use solutions having reduced or substantially nohydrogen peroxide are introduced to a water source in need of treatment.

The methods by which the peroxyformic acid solutions are introduced intothe aqueous fluids according to the invention are not critical.Introduction of the peroxyformic acid compositions may be carried out ina continuous or intermittent manner and will depend on the type of waterbeing treated. In some embodiments, the peroxyformic acid compositionsare introduced into an aqueous fluid according to the methods disclosedin U.S. patent application Ser. No. 13/645,671, titled “New Method andArrangement for Feeding Chemicals into a Hydrofracturing Process and Oiland Gas Applications”, which is hereby incorporated by reference in itsentirety.

In some embodiments, the water source treated by the present methodsdoes not comprise reuse water, the treated water source comprises fromabout 10 ppm to about 20 ppm of the in situ formed peroxyformic acid andfrom about 1 ppm to about 2 ppm of hydrogen peroxide and the treatedwater source does not comprise a friction reducer and/or a rheologymodifier.

In some embodiments, the water source treated by the present methods isa blended water source that comprises about 80 wt-% fresh water or pondwater and about 20 wt-% of reuse water, the treated water sourcecomprises from about 25 ppm to about 35 ppm of the in situ formedperoxyformic acid and from about 2 ppm to about 3 ppm of hydrogenperoxide and catalase, the treated water source does not comprise afriction reducer and/or a rheology modifier, and the treated watersource is formed before reaching a blending tub.

In some embodiments, the water source treated by the present methods isa blended water source that comprises about 80 wt-% fresh water or pondwater and about 20 wt-% of reuse water, the treated water sourcecomprises from about 25 ppm to about 35 ppm of the in situ formedperoxyformic acid and from about 2 ppm to about 3 ppm of hydrogenperoxide and catalase, the treated water source comprises a frictionreducer and/or a rheology modifier, and the treated water source isformed in a blending tub.

In some embodiments, the treated water source comprises from about 30ppm or less of the in situ formed peroxyformic acid and about 0.5 ppm orless of the hydrogen peroxide, the treated water source comprises afriction reducer and/or a rheology modifier, and the treated watersource is directed into or is at a subterranean environment.

In some aspects, the methods disclosed for water treatment in oil andgas recovery provide effective antimicrobial efficacy withoutdeleterious interaction with functional agents, including for examplefriction reducers. In a further aspect, the methods for water treatmentprovide increased antimicrobial efficacy compared to the use of theantimicrobial peracids alone. In a still further aspect, the methods ofuse result in the disposal of cleaner water with low numbers ofmicroorganisms. In yet a further aspect of the methods of the invention,the reduction and/or elimination of H₂O₂ from the peracid compositionsminimizes the negative effects of the oxidant H₂O₂. Still further, themethods of the invention reduce the volume expansion within sealedsystems used in oil and gas recovery methods, as a result of thereduction and/or elimination of H₂O₂ from the systems.

In an aspect, the peroxyformic acid solutions are added to waters inneed of treatment prior to the drilling and fracking steps in order torestrict the introduction of microbes into the reservoir and to preventthe microbes from having a negative effect on the integrity of thefluids. The treatment of source waters (e.g. pond, lake, municipal,etc.) and/or produced waters is particularly well suited for useaccording to the invention.

The treated waters according to the invention can be used for both slickwater fracturing (i.e. using frictions reducers) and/or gel fracturing(i.e. using viscosity enhancers), depending on the type of formationbeing fractured and the type of hydrocarbon expected to be produced. Useof a peroxyformic acid solution, including a catalase treatedperoxyformic acid composition use solution having low to substantiallyno hydrogen peroxide, is suitable for both slick water fracturing andgel fracturing.

In an aspect, pretreating the peroxyformic acid composition withcatalase substantially removes the hydrogen peroxide with minimal to noimpact on the fracturing fluids and the well itself. In an aspect, theperoxyformic acid composition pretreated with catalase allows theformation of gel suitable for gel fracturing, as opposed to untreatedperoxyformic acid composition solutions that do not allow a gel to formunder certain conditions. In a further aspect, the peroxyformic acidcomposition solutions are added to waters in need of treatment in thesubterranean well formations (e.g. introduced through a bore hole in asubterranean formation). These methods provide additional control withinthe well formation suitable for reducing microbial populations alreadypresent within the down hole tubing in the well or within the reservoiritself.

In a still further aspect, the peroxyformic acid composition solutionsare added to waters in need of treatment before disposal. In such anaspect, flow back waters (e.g. post fracking) are treated to minimizemicrobial contaminations in the waters and to remove solids prior todisposal of the water into a subterranean well, reuse in a subsequentfracturing application or return of the water into local environmentalwater sources.

In an aspect, the water source in need of treatment may varysignificantly. For example, the water source may be a freshwater source(e.g. pond water), salt water or brine source, brackish water source,recycled water source, or the like. In an aspect, wherein offshore welldrilling operations are involved, seawater sources are often employed(e.g. saltwater or non-saltwater). Beneficially, the peroxyformic acidcompositions, with or without catalase, of the invention are suitablefor use with any types of water and provide effective antimicrobialefficiency with any of such water sources.

Large volumes of water are employed according to the invention asrequired in well fluid operations. As a result, in an aspect of theinvention, recycled water sources (e.g. produced waters) are oftenemployed to reduce the amount of a freshwater, pond water or seawatersource required. Recycled or produced water are understood to includenon-potable water sources. The use of such produced waters (incombination with freshwater, pond water or seawater) reduces certaineconomic and/or environmental constraints. In an aspect of theinvention, thousands to millions of gallons of water may be employed andthe combination of produced water with fresh water sources providessignificant economic and environmental advantages. In an aspect of theinvention, as much produced water as practical is employed. In anembodiment at least 1% produced water is employed, preferably at least5% produced water is employed, preferably at least 10% produced water isemployed, preferably at least 20% produced water is employed, or morepreferably more than 20% produced water is employed.

In an aspect of the invention, the method includes a pretreatment step,wherein the peroxyformic acid composition is treated with a catalaseenzyme to reduce the hydrogen peroxide concentration in a use solution.The pretreatment step occurs prior to combining the peracidantimicrobial composition and/or catalase to a water source in need oftreatment. In an aspect of the invention, the pretreatment may occurwithin a few minutes to hours before addition to a water source.

According to embodiments of the invention, a sufficient amount of theperoxyformic acid composition, with or without catalase, is added to theaqueous water source in need of treatment to provide the desiredperoxyformic acid concentration for antimicrobial efficacy. For example,a water source is dosed amounts of the peroxyformic acid and catalaseuse solution composition until a peroxyformic acid concentration withinthe water source is detected within the preferred concentration range(e.g. about 1 ppm to about 100 ppm peracid). In an aspect, it ispreferred to have a microbial count of less than about 100,000microbes/mL, more preferably less than about 10,000 microbes/mL, or morepreferably less than about 1,000 microbes/mL.

The methods of use as described herein can vary in the temperature andpH conditions associated with use of the aqueous treatment fluids. Forexample, the aqueous treatment fluids may be subjected to varyingambient temperatures according to the applications of use disclosedherein, including ranging from about 0 C to about 130 C in the course ofthe treatment operations. Preferably, the temperature range is betweenabout 5 C to about 100 C, more preferably between about 10 C to about 80C. However, as a majority of the antimicrobial activity of thecompositions of the invention occurs over a short period of time, theexposure of the compositions to relatively high temperatures is not asubstantial concern. In addition, the peracid composition aqueoustreatment fluids (i.e. use solutions) may be subjected to varying pHranges, such as from 1 to about 10.5. Preferably, the pH range is lessthan about 9, less than about 7.2 (pKa value of performic acid) toensure the effective antimicrobial efficacy of the peracid.

The antimicrobial compositions of the invention are fast-acting.However, the present methods require a certain minimal contact time ofthe compositions with the water in need of treatment for occurrence ofsufficient antimicrobial effect. The contact time can vary withconcentration of the use compositions, method of applying the usecompositions, temperature of the use compositions, pH of the usecompositions, amount of water to be treated, amount of soil orsubstrates in the water to be treated, or the like. The contact orexposure time can be at least about 15 seconds. In some embodiments, theexposure time is about 1 to 5 minutes. In other embodiments, theexposure time is at least about 10 minutes, 30 minutes, or 60 minutes.In other embodiments, the exposure time is a few minutes to hours. Thecontact time will further vary based upon the concentration of peracidin a use solution.

Beneficial Effects of the Methods of Use in Water Treatment

In an aspect, the methods of use provide an antimicrobial for use thatdoes not negatively impact the environment. Beneficially, thedegradation of the compositions of the invention provides a “green”alternative.

In a further aspect, the methods of use provide an antimicrobial for usethat does not negatively interfere with friction reducers, viscosityenhancers and/or other functional ingredients. In a further aspect, themethods of use do not negatively interfere with any additionalfunctional agents utilized in the water treatment methods, including forexample, corrosion inhibitors, descaling agents and the like. Thecompositions administered according to the invention provide extremelyeffective control of microorganisms without adversely affecting thefunctional properties of any additive polymers of an aqueous system. Inaddition, the peroxyformic acid compositions provide additional benefitsto a system, including for example, reducing corrosion within the systemdue to the decreased or substantially eliminated hydrogen peroxide froma treated composition. Beneficially, the non-deleterious effects of theperoxyformic acid compositions (with or without a catalase) on thevarious functional ingredients used in water treatment methods areachieved regardless of the make-up of the water source in need oftreatment.

In an additional aspect, the methods of use prevent the contamination ofsystems, such as well or reservoir souring. In further aspects, themethods of use prevent microbiologically-influenced corrosion of thesystems upon which it is employed.

In further aspects, the methods of use employ the antimicrobial and/orbleaching activity of the peroxyformic acid compositions. For example,the invention includes a method for reducing a microbial populationand/or a method for bleaching. These methods can operate on an article,surface, in a body or stream of water or a gas, or the like, bycontacting the article, surface, body, or stream with the compositions.Contacting can include any of numerous methods for applying thecompositions, including, but not limited to, providing the antimicrobialperoxyformic acid compositions in an aqueous use solution and immersingany articles, and/or providing to a water source in need of treatment.

The compositions are suitable for antimicrobial efficacy against a broadspectrum of microorganisms, providing broad spectrum bactericidal andfungistatic activity. For example, the peracid biocides of thisinvention provide broad spectrum activity against wide range ofdifferent types of microorganisms (including both aerobic and anaerobicmicroorganisms), including bacteria, yeasts, molds, fungi, algae, andother problematic microorganisms associated with oil- and gas-fieldoperations.

Exemplary microorganisms susceptible to the peracid compositions of theinvention include, gram positive bacteria (e.g., Staphylococcus aureus,Bacillus species (sp.) like Bacillus subtilis, Clostridia sp.), gramnegative bacteria (e.g., Escherichia coli, Pseudomonas sp., Klebsiellapneumoniae, Legionella pneumophila, Enterobacter sp., Serratia sp.,Desulfovibrio sp., and Desulfotomaculum sp.), yeasts (e.g.,Saccharomyces cerevisiae and Candida albicans), molds (e.g., Aspergillusniger, Cephalosporium acremonium, Penicillium notatum, and Aureobasidiumpullulans), filamentous fungi (e.g., Aspergillus niger and Cladosporiumresinae), algae (e.g., Chlorella vulgaris, Euglena gracilis, andSelenastrum capricornutum), and other analogous microorganisms andunicellular organisms (e.g., phytoplankton and protozoa). Otherexemplary microorganisms susceptible to the peracid compositions of theinvention include the exemplary microorganisms disclosed in U.S. patentapplication US 2010/0160449 A1, e.g., the sulfur- or sulfate-reducingbacteria, such as Desulfovibrio and Desulfotomaculum species.

Use in Other Treatments

Additional embodiments of the invention include water treatments forvarious industrial processes for treating liquid systems. As usedherein, “liquid system” refers to flood waters or an environment withinat least one artificial artifact, containing a substantial amount ofliquid that is capable of undergoing biological fouling. Liquid systemsinclude but are not limited to industrial liquid systems, industrialwater systems, liquid process streams, industrial liquid processstreams, industrial process water systems, process water applications,process waters, utility waters, water used in manufacturing, water usedin industrial services, aqueous liquid streams, liquid streamscontaining two or more liquid phases, and any combination thereof.

In a further aspect, the present methods can also be used to treat otherliquid systems where both the compositions' antimicrobial function andoxidant properties can be utilized. Aside from the microbial issuessurrounding waste water, waste water is often rich in malodorouscompounds of reduced sulfur, nitrogen or phosphorous. A strong oxidantsuch as the compositions disclosed herein converts these compoundsefficiently to their odor free derivatives e.g. the sulfates, phosphatesand amine oxides. These same properties are very useful in the pulp andpaper industry where the property of bleaching is also of great utility.

The present methods can be conducted at any suitable temperature. Insome embodiments, the present methods are conducted at a temperatureranging from about −2° C. to about 70° C., e.g., from about 0° C. toabout 4° C. or 5° C., from about 5° C. to about 10° C., from about 11°C. to about 20° C., from about 21° C. to about 30° C., from about 31° C.to about 40° C., including at about 37° C., from about 41° C. to about50° C., from about 51° C. to about 60° C., or from about 61° C. to about70° C.

The present methods can be used in the methods, processes or proceduresdescribed and/or claimed in U.S. Pat. Nos. 5,200,189, 5,314,687 and5,718,910. In some embodiments, the present methods can be used ofsanitizing facilities or equipment comprises the steps of contacting thefacilities or equipment with the composition of the present invention ata temperature in the range of about 4° C. to about 60° C. Theperoxyformic acid composition is then circulated or left in contact withthe facilities or equipment for a time sufficient to sanitize (generallyat least 30 seconds) and the treated target composition is thereafterdrained or removed from the facilities or equipment.

As noted above, the present methods are useful in the cleaning orsanitizing of processing facilities or equipment in the food service,food processing or health care industries. Examples of processfacilities in which the present methods can be employed include a milkline dairy, a continuous brewing system, food processing lines such aspumpable food systems and beverage lines, etc. Food service wares canalso be disinfected with the present methods. The present methods arealso useful in sanitizing or disinfecting solid surfaces such as floors,counters, furniture, medical tools and equipment, etc., found in thehealth care industry. Such surfaces often become contaminated withliquid body spills such as blood, other hazardous body fluids ormixtures thereof.

Generally, the actual cleaning of the in-place system or other surface(i.e., removal of unwanted offal therein) can be accomplished with adifferent material such as a formulated detergent which is introducedwith heated water. After this cleaning step, the peroxyformic acidcomposition can be applied or introduced into the system at a usesolution concentration in unheated, ambient temperature water. In someembodiments, the peroxyformic acid composition is found to remain insolution in cold (e.g., 40° F./4° C.) water and heated (e.g., 140°F./60° C.) water. Although it is not normally necessary to heat theaqueous use solution of the peroxyformic acid composition, under somecircumstances heating may be desirable to further enhance itsantimicrobial activity.

In some embodiments, a method of sanitizing substantially fixed in-placeprocess facilities comprises the following steps. The peroxyformic acidcomposition of the present invention is introduced into the processfacilities at a temperature in the range of about 4° C. to about 60° C.After introduction of the use solution, the solution is circulatedthroughout the system for a time sufficient to sanitize the processfacilities (i.e., to kill undesirable microorganisms). After the systemhas been sanitized by means of the present composition, the usecomposition or solution is drained from the system. Upon completion ofthe sanitizing step, the system optionally may be rinsed with othermaterials such as potable water. The present composition is preferablycirculated through the process facilities for 10 minutes or less.

In other embodiments, the present peroxyformic acid composition may alsobe employed by dipping food processing equipment into the diluted (oruse) composition or solution of the present invention, soaking theequipment for a time sufficient to sanitize the equipment, and wiping ordraining excess solution off the equipment. The composition may befurther employed by spraying or wiping food processing surfaces with theuse solution, keeping the surfaces wet for a time sufficient to sanitizethe surfaces, and removing the excess composition or solution by wiping,draining vertically, vacuuming, etc.

In still other embodiments, the present peroxyformic acid compositionmay also be used in a method of sanitizing hard surfaces such asinstitutional type equipment, utensils, dishes, health care equipment ortools, and other hard surfaces. The present peroxyformic acidcomposition may also be employed in sanitizing clothing items or fabricwhich has become contaminated. The peroxyformic acid composition iscontacted with any of the above contaminated surfaces or items at usetemperatures in the range of about 4° C. to about 60° C. for a period oftime effective to sanitize, disinfect, or sterilize the surface or item.

The present methods can be used in the methods, processes or proceduresdescribed and/or claimed in U.S. Pat. Nos. 6,165,483 and 6,238,685B1, totreat field or greenhouse grown plant tissue, seeds, fruits, and growingmedia and containers. The present peroxyformic acid composition canlower the natural, plant pathogen and human pathogenic microbial loadresulting in less waste to molding, spoilage, and destruction because ofpathogenic poisons.

In some embodiments, the present peroxyformic acid composition can beused to protect growing plant tissue from the undesirable effects ofmicrobial attack. The present peroxyformic acid composition can beapplied to growing plant tissues and can provide residual antimicrobialeffects after the plant has completed its growth cycle, fruit orvegetable material have been harvested and sent to market. The presentcomposition can be an effective treatment of living or growing planttissues including seeds, roots, tubers, seedlings, cuttings, rootingstock, growing plants, produce, fruits and vegetables, etc. Undercertain circumstances, a single peroxyacid material can be effective,however, in other circumstances, a mixed peroxy acid has substantiallyimproved and surprising properties.

In some embodiments, the composition used in the present methods alsomay contain a hydrotrope for the purpose of increasing the aqueoussolubility of various slightly soluble organic compounds. The preferredembodiment of the composition utilizes a hydrotrope chosen from thegroup of n-octanesulfonate, a xylene sulfonate, a naphthalene sulfonate,ethylhexyl sulfate, lauryl sulfate, an amine oxide, or a mixturethereof.

In some embodiments, the composition used in the present methods mayalso contain a chelating agent for the purpose of removing ions fromsolution. The preferred embodiment of the invention uses1-hydroxyethylidene-1,1-diphosphonic acid.

The present methods can be used in the methods, processes or proceduresdescribed and/or claimed in U.S. Pat. Nos. 6,010,729, 6,103,286,6,545,047 and 8,030,351 for sanitizing animal carcasses.

In some embodiments, the compositions of the present invention can beused in a method of treating animal carcasses to obtain a reduction byat least one log₁₀ in surface microbial population which method includesthe step of treating said carcass with a composition of the presentinvention comprising an effective antimicrobial amount comprising atleast 2 parts per million (ppm, parts by weight per each one millionparts) of one or more peroxycarboxylic acids having up to 12 carbonatoms, an effective antimicrobial amount comprising at least 20 ppm ofone or more carboxylic acids having up to 18 carbon atoms, and the firstand second stabilizing agents described above, to reduce the microbialpopulation.

In yet other embodiments, the present invention is directed to a methodof treating an animal carcass to reduce a microbial population inresulting cut meat, the method comprising the steps of spraying anaqueous antimicrobial treatment composition onto said carcass at apressure of at least 50 psi at a temperature of up to about 60° C.resulting in a contact time of at least 30 seconds, the antimicrobialcomposition comprising an effective antimicrobial amount comprisingleast 2 ppm of one or more carboxylic acid, peroxycarboxylic acid ormixtures thereof, and the first and second stabilizing agents describedabove; and achieving at least a one log₁₀ reduction in the microbialpopulation.

In yet other embodiments, the present invention is directed to a methodof treating an animal carcass to reduce a microbial population inresulting cut meat, the method comprising the steps of placing theanimal carcass in a chamber at atmospheric pressure; filling the chamberwith condensing steam comprising an antimicrobial composition, e.g., adiluted composition of the present invention, for a short duration; andquickly venting and cooling the chamber to prevent browning of the meatcarcass; wherein the duration of the steam thermal process may be fromabout 5 seconds to about 30 seconds and the chamber temperature mayreach from about 50° C. to about 93° C.

The antimicrobial composition can be applied in various ways to obtainintimate contact with each potential place of microbial contamination.For example, it can be sprayed on the carcasses, or the carcasses can beimmersed in the composition. Additional methods include applying afoamed composition and a thickened or gelled composition. Vacuum and orlight treatments can be included, if desired, with the application ofthe antimicrobial composition. Thermal treatment can also be applied,either pre-, concurrent with or post application of the antimicrobialcomposition.

One preferred spray method for treating carcasses with dilutedcompositions of the present invention involves spraying the carcass withan aqueous spray at a temperature less than about 60° C. at a pressureof about 50 to 500 psi gauge wherein the spray comprises an effectiveantimicrobial amount of a carboxylic acid, an effective antimicrobialamount of a peroxycarboxylic acid or mixtures thereof, and the first andsecond stabilizing agents described above. These sprays can also containan effective portion of a peroxy compound such as hydrogen peroxide andother ingredients such as sequestering agents, etc. The high pressurespray action of the aqueous treatment can remove microbial populationsby combining the mechanical action of the spray with the chemical actionof the antimicrobial materials to result in an improved reduction ofsuch populations on the surface of the carcass.

All pressures are psig (or psi gauge). In some embodiments,differentiation of antimicrobial “-cidal” or “-static” activity, thedefinitions which describe the degree of efficacy, and the officiallaboratory protocols for measuring this efficacy are importantconsiderations for understanding the relevance of antimicrobial agentsin compositions. Antimicrobial compositions may affect two kinds ofmicrobial cell damages. The first is a truly lethal, irreversible actionresulting in complete microbial cell destruction or incapacitation. Thesecond type of cell damage is reversible, such that if the organism isrendered free of the agent, it can again multiply. The former is termedbacteriocidal and the latter, bacteriostatic. A sanitizer and adisinfectant are, by definition, agents which provide antibacterial orbacteriocidal activity and may achieve at least a five-fold reduction(i.e., a five log 10 reduction) in microbial populations after a 30second contact time (see AOAC method 960.09).

The present methods can be used in the methods, processes or proceduresdescribed and/or claimed in U.S. Pat. Nos. 8,017,409 and 8,236,573. Insome embodiments, the present methods may be used for a variety ofdomestic or industrial applications, e.g., to reduce microbial or viralpopulations on a surface or object or in a body or stream of water. Theperoxyformic acid compositions of the present invention may be appliedin a variety of areas including kitchens, bathrooms, factories,hospitals, dental offices and food plants, and may be applied to avariety of hard or soft surfaces having smooth, irregular or poroustopography. Suitable hard surfaces include, for example, architecturalsurfaces (e.g., floors, walls, windows, sinks, tables, counters andsigns); eating utensils; hard-surface medical or surgical instrumentsand devices; and hard-surface packaging. Such hard surfaces may be madefrom a variety of materials including, for example, ceramic, metal,glass, wood or hard plastic. Suitable soft surfaces include, for examplepaper; filter media, hospital and surgical linens and garments;soft-surface medical or surgical instruments and devices; andsoft-surface packaging. Such soft surfaces may be made from a variety ofmaterials including, for example, paper, fiber, woven or non-wovenfabric, soft plastics and elastomers. The diluted (or use) compositionsmay also be applied to soft surfaces such as food and skin (e.g., ahand). The diluted (or use) compositions may be employed as a foaming ornon-foaming environmental sanitizer or disinfectant.

In other embodiments, the peroxyformic acid compositions of the presentinvention may be included in products such as sterilants, sanitizers,disinfectants, preservatives, deodorizers, antiseptics, fungicides,germicides, sporicides, virucides, detergents, bleaches, hard surfacecleaners, hand soaps, waterless hand sanitizers, and pre- orpost-surgical scrubs.

In still other embodiments, the peroxyformic acid compositions of thepresent invention may also be used in veterinary products such asmammalian skin treatments or in products for sanitizing or disinfectinganimal enclosures, pens, watering stations, and veterinary treatmentareas such as inspection tables and operation rooms. The peroxyformicacid compositions may be employed in an antimicrobial foot bath forlivestock or people.

In yet other embodiments, the present methods may be employed forreducing the population of pathogenic microorganisms, such as pathogensof humans, animals, and the like. Exemplary pathogenic microorganismsinclude fungi, molds, bacteria, spores, and viruses, for example, S.aureus, E. coli, Streptococci, Legionella, Pseudomonas aeruginosa,mycobacteria, tuberculosis, phages, or the like. Such pathogens maycause a varieties of diseases and disorders, including Mastitis or othermammalian milking diseases, tuberculosis, and the like. The presentmethods may be used to reduce the population of microorganisms on skinor other external or mucosal surfaces of an animal. In addition, thepresent methods may be used to kill pathogenic microorganisms thatspread through transfer by water, air, or a surface substrate. In someapplications, the compositions of the present invention need only beapplied to the skin, other external or mucosal surfaces of an animalwater, air, or surface.

In yet other embodiments, the present methods may also be used on foodsand plant species to reduce surface microbial populations; used atmanufacturing or processing sites handling such foods and plant species;or used to treat process waters around such sites. For example, thepresent methods may be used on food transport lines (e.g., as beltsprays); boot and hand-wash dip-pans; food storage facilities;anti-spoilage air circulation systems; refrigeration and coolerequipment; beverage chillers and warmers, blanchers, cutting boards,third sink areas, and meat chillers or scalding devices. The presentmethods may be used to treat transport waters such as those found influmes, pipe transports, cutters, slicers, blanchers, retort systems,washers, and the like. Particular foodstuffs that may be treated withthe present methods include eggs, meats, seeds, leaves, fruits andvegetables. Particular plant surfaces include both harvested and growingleaves, roots, seeds, skins or shells, stems, stalks, tubers, corms,fruit, and the like. The present methods may also be used to treatanimal carcasses to reduce both pathogenic and non-pathogenic microbiallevels.

In yet other embodiments, the present methods may be useful in thecleaning or sanitizing of containers, processing facilities, orequipment in the food service or food processing industries. The presentmethods may be used on food packaging materials and equipment, includingfor cold or hot aseptic packaging. Examples of process facilities inwhich the present methods may be employed include a milk line dairy, acontinuous brewing system, food processing lines such as pumpable foodsystems and beverage lines, etc. Food service wares may be disinfectedwith the present methods. For example, the present methods may also beused on or in ware wash machines, dishware, bottle washers, bottlechillers, warmers, third sink washers, cutting areas (e.g., waterknives, slicers, cutters and saws) and egg washers. Particular treatablesurfaces include packaging such as cartons, bottles, films and resins;dish ware such as glasses, plates, utensils, pots and pans; ware washmachines; exposed food preparation area surfaces such as sinks,counters, tables, floors and walls; processing equipment such as tanks,vats, lines, pumps and hoses (e.g., dairy processing equipment forprocessing milk, cheese, ice cream and other dairy products); andtransportation vehicles. Containers include glass bottles, PVC orpolyolefin film sacks, cans, polyester, PEN or PET bottles of variousvolumes (100 ml to 2 liter, etc.), one gallon milk containers, paperboard juice or milk containers, etc.

In yet other embodiments, the present methods may also be used on or inother industrial equipment and in other industrial process streams suchas heaters, cooling towers, boilers, retort waters, rinse waters,aseptic packaging wash waters, and the like. The present methods may beused to treat microbes and odors in recreational waters such as inpools, spas, recreational flumes and water slides, fountains, and thelike.

In yet other embodiments, a filter containing the peroxyformic acidcompositions of the present invention may be used to reduce thepopulation of microorganisms in air and liquids. Such a filter may beused to remove water and air-born pathogens such as Legionella.

In yet other embodiments, the present methods may be employed forreducing the population of microbes, fruit flies, or other insect larvaon a drain or other surface.

In yet other embodiments, the present methods may also be employed bydipping food processing equipment into the peroxyformic acid compositionor solution of the present invention, soaking the equipment for a timesufficient to sanitize the equipment, and wiping or draining excesscomposition or solution off the equipment. The present methods may befurther employed by spraying or wiping food processing surfaces with theperoxyformic acid composition or solution, keeping the surfaces wet fora time sufficient to sanitize the surfaces, and removing excesscomposition or solution by wiping, draining vertically, vacuuming, etc.

In yet other embodiments, the present methods may also be used forsanitizing hard surfaces such as institutional type equipment, utensils,dishes, health care equipment or tools, and other hard surfaces. Thepresent methods may also be employed in sanitizing clothing items orfabrics which have become contaminated. The peroxyformic acidcompositions of the present invention can be contacted with anycontaminated surfaces or items at use temperatures in the range of about4° C. to 60° C., for a period of time effective to sanitize, disinfect,or sterilize the surface or item. For example, the peroxyformic acidcompositions may be injected into the wash or rinse water of a laundrymachine and contacted with contaminated fabric for a time sufficient tosanitize the fabric. Excess composition may be removed by rinsing orcentrifuging the fabric.

In yet other embodiments, the peroxyformic acid compositions of thepresent invention may be applied to microbes or to soiled or cleanedsurfaces using a variety of methods. These methods may operate on anobject, surface, in a body or stream of water or a gas, or the like, bycontacting the object, surface, body, or stream with the diluted (oruse) composition. Contacting may include any of numerous methods forapplying a composition, such as spraying the composition, immersing theobject in the composition, foam or gel treating the object with thecomposition, or a combination thereof.

In yet other embodiments, the peroxyformic acid compositions of thepresent invention may be employed for bleaching pulp. The compositionsmay be employed for waste treatment. Such a composition may includeadded bleaching agent.

In yet other embodiments, other hard surface cleaning applications forthe peroxyformic acid compositions of the present invention includeclean-in-place systems (CIP), clean-out-of-place systems (COP),washer-decontaminators, sterilizers, textile laundry machines, ultra andnano-filtration systems and indoor air filters. COP systems may includereadily accessible systems including wash tanks, soaking vessels, mopbuckets, holding tanks, scrub sinks, vehicle parts washers,non-continuous batch washers and systems, and the like.

The concentrations of peroxyformic acid and/or hydrogen peroxide in theperoxyformic acid compositions of the present invention can be monitoredin any suitable manner. In some embodiments, the concentrations ofperoxyformic acid and/or hydrogen peroxide in the peroxyformic acidand/or hydrogen peroxide compositions can be monitored using a kineticassay procedure, e.g., the exemplary procedure disclosed in U.S. Pat.Nos. 8,017,409 and 8,236,573. This can be accomplished by exploiting thedifference in reaction rates between peroxyformic acid and hydrogenperoxide when using, for example, a buffered iodide reagent todifferentiate peroxyformic acid and hydrogen peroxide concentrationswhen both these analyte compounds are present in the use composition.The monitor may also determine the concentrations of peroxyformic acidand/or hydrogen peroxide in the presence of other additionalingredients, such as acidulants, one or more stabilizing agents,nonionic surfactants, semi-polar nonionic surfactants, anionicsurfactants, amphoteric or ampholytic surfactants, adjuvants, solvents,additional antimicrobial agents or other ingredients which may bepresent in the use composition.

Methods for Treating a Biofilm

In yet another aspect, the present invention is directed to a method fortreating a biofilm, which method comprises contacting a biofilm on asurface with an effective amount of peroxyformic acid for a sufficienttime to stabilize, reduce and/or remove microbial population in and/oron said treated biofilm, or to stabilize, reduce and/or remove saidbiofilm on said surface.

The present methods can be used to treat a biofilm in any suitablelocation or environment. In some embodiments, the present methods can beused to treat a biofilm located on or inside a human environment, suchas a biofilm located on or inside a shower room or site, a water pipe, asewage pipe, a floor, a counter, or a part of human body. For example,the present methods can be used to treat a biofilm located on or insidea dental plaque, a part of a urinary tract, a part of a middle ear, or apart of gums. In other embodiments, the present methods can be used totreat a biofilm located on or inside a cooling- or heating-water system.In still other embodiments, the present methods can be used to treat abiofilm located on or inside an engineering system, e.g., a pipeline ofoil and gas industry. In still other embodiments, the present methodscan be used to treat a biofilm located on or inside a vehicle, e.g., anautomobile, a boat or a ship. In yet other embodiments, the presentmethods can be used to treat a biofilm located on or inside a plant. Inyet other embodiments, the present methods can be used to treat abiofilm located on or inside a consumer product, e.g., a contact lens ora pair glasses. In yet other embodiments, the present methods can beused to treat a biofilm located on or inside a medical device, e.g., animplantable medical device. Exemplary implantable medical devicesinclude a catheter, a prosthetic cardiac valve or an intrauterinedevice. In yet other embodiments, the present methods can be used totreat a biofilm located on or inside a membrane, e.g., anultrafiltration membrane (UF) membrane.

The present methods can use any suitable concentration of peroxyformicacid. In some embodiments, the present methods can comprise contacting abiofilm on a surface with from about 10 ppm to about 1,000 ppmperoxyformic acid, e.g., 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm,50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm,150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm,700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, or950-1,000 ppm peroxyformic acid.

The present methods can comprise contacting a biofilm on a surface withan effective amount of peroxyformic acid for any suitable amount oftime. In some embodiments, the present methods can comprise contacting abiofilm on a surface with an effective amount of peroxyformic acid forfrom about 1 minute to about 10 hours, e.g., about 1 minute, 2 minutes,3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9minutes, 10 minutes, 20 minutes, 30 minutes, 40 minutes, 50 minutes, 1hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9hours, or 10 hours. In an aspect, the contacting occurs for a period oftime before degradation of the peroxyformic acid composition.

The present methods can be used to treat a biofilm made of or from anysuitable microbial population. In some embodiments, the present methodcan be used to treat a biofilm made of or from a prokaryotic microbialpopulation, e.g., a bacterial or an archaeal population. Exemplarybacterial populations include a population of Pseudomonas aeruginosa,Streptococcus mutans, Streptococcus pneumoniae, a Legionella bacteria,or a Bacillus bacteria, e.g., Bacillus sp. Spore. In other embodiments,the present method can be used to treat a biofilm made of or from aneukaryotic microbial population, e.g., a protozoal or fungal population.In still other embodiments, the present method can be used to treat abiofilm made of or from a viral population.

The peroxyformic acid used in the present methods can be prepared usingany suitable methods as disclosed herein according to the invention. Inan embodiment, the peroxyformic acid used in the present methods can beprepared by contacting an ester of a polyhydric alcohol and formic acid,with hydrogen peroxide or a substance that generates hydrogen peroxidewhen in contact with a liquid. For example, the peroxyformic acid usedin the present methods can be prepared using any of the peroxyformicacid forming compositions described above or any of the methodsdescribed above. In other embodiments, the peroxyformic acid used in thepresent methods can be prepared in situ for the application of theformed peroxyformic acid.

In some embodiments, the present methods can further comprise contactingthe biofilm with a C₂-C₂₂ percarboxylic acid. Exemplary C₂-C₂₂percarboxylic acids include peroxyacetic acid, peroxyoctanoic acidand/or peroxysulfonated oleic acid. In other embodiments, the presentmethods can further comprise contacting the biofilm with a surfactant.Exemplary surfactants include an anionic surfactant, a nonionicsurfactant, a cationic surfactant as well as an amphoteric surfactant.In still other embodiments, the present methods can further comprisecontacting the biofilm with a solvent. Exemplary solvents include analcohol, an ester, a glycol ether, an amide, a hydrocarbon etc. In stillother embodiments, the present methods can further comprise contactingthe biofilm with an enzyme.

In some embodiments, the present methods can further comprise assessingthe efficacy of the method for treating a biofilm. The efficacy of thepresent methods can be assessed using any suitable methods. For example,the efficacy of the present methods can be assessed using a biofilmreactor. Exemplary biofilm reactors include a Center for Disease Control(CDC) biofilm reactor or a Rotating Disk Reactor (RDR) biofilm reactor.The biofilm reactor can comprise a surface or disc coupon, e.g., apolycarbonate coupon.

Methods for High Level Disinfecting, e.g. Endoscope and Other InstrumentReprocessing

In yet another aspect, the various methods for treatment using theperoxyformic acid generated according to the methods of the inventioncan be employed for high level disinfectant applications, includingsterilizing medical devices. The rate of formation of the peroxyformicacid in situ is particularly beneficial for the application of use forhigh level disinfection. The disinfectant is generated in situ andprovides on demand disinfectant. Beneficially, the methods employing thehigh level disinfectant do not require high pressure and temperaturerequired to achieve sterility. In an embodiment, the surface, such as aninstrument, in need of treatment is contacted with an effective amountof peroxyformic acid for a sufficient time to stabilize, reduce and/orremove microbial population in and/or on said treated surface, or tostabilize, reduce and/or remove soils and microbes on said surface.

In an aspect, the methods allow for repurposing or reuse of the surfacethrough disinfection and/or sanitizing of the surface, such as aninstrument. Exemplary surfaces, including instruments suitable forreprocessing according to the invention include any instrument,including medical or dental instruments or devices that can benefit fromcleaning with a composition according to the present invention.Particularly suitable instruments include, but are not limited to:diagnostic instruments, scopes (e.g., endoscopes, stethoscopes, andarthoscopes) and related equipment, and the like, or combinationsthereof. Various conventional reprocessing methods which are suitablefor use with the peroxyformic acid generated in situ are disclosed inU.S. Pat. Nos. 4,721,123 and 5,310,524, each of which are incorporatedherein by reference in their entirety.

The present methods can use any suitable concentration of peroxyformicacid. In some embodiments, the present methods can comprise contacting asurface with from about 10 ppm to about 1,000 ppm peroxyformic acid,e.g., 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm, 50-60 ppm, 60-70 ppm,70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm, 150-200 ppm, 200-250 ppm,250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450 ppm, 450-500 ppm, 500-550ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm, 700-750 ppm, 750-800 ppm,800-850 ppm, 850-900 ppm, 900-950 ppm, or 950-1,000 ppm peroxyformicacid. In a preferred aspect, the methods of contacting provide fromabout 10 ppm to about 500 ppm peroxyformic acid for high leveldisinfectant generated in situ within a matter of minutes.

The present methods can comprise contacting a surface with an effectiveamount of peroxyformic acid for any suitable amount of time. In someembodiments, the present methods can comprise contacting a surface withan effective amount of peroxyformic acid for from about 1 minute toabout an hour, e.g., about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes orgreater. In an aspect, the contacting time is preferably less than 10minutes, and more preferably less than 5 minutes. In an aspect, thecontacting occurs for a period of time before degradation of theperoxyformic acid composition.

The present methods can be used to treat a surface for instrumentreprocessing having a contaminated surface from any suitable microbialpopulations. In some embodiments, the present method can be used totreat a surface made of or from a prokaryotic microbial population,e.g., a bacterial or an archaeal population. Exemplary bacterialpopulations include a population of Pseudomonas aeruginosa,Streptococcus mutans, Streptococcus pneumoniae, a Legionella bacteria,or a Bacillus bacteria, e.g., Bacillus sp. Spore. In other embodiments,the present method can be used to treat a surface made of or from aneukaryotic microbial population, e.g., a protozoal or fungal population.In still other embodiments, the present method can be used to treat asurface made of or from a viral population.

The peroxyformic acid used in the present methods can be prepared usingany suitable methods disclosed herein. In some embodiments, theperoxyformic acid used in the present methods can be prepared bycontacting an ester of a polyhydric alcohol and formic acid, withhydrogen peroxide or a substance that generates hydrogen peroxide whenin contact with a liquid. For example, the peroxyformic acid used in thepresent methods can be prepared using any of the peroxyformic acidforming compositions described above or any of the methods describedabove. In other embodiments, the peroxyformic acid used in the presentmethods can be prepared in situ for the application of the formedperoxyformic acid.

In some embodiments, the present methods can further comprise contactingthe surface with the peroxyformic acid and a C₂-C₂₂ percarboxylic acid.Exemplary C₂-C₂₂ percarboxylic acids include peroxyacetic acid,peroxyoctanoic acid and/or peroxysulfonated oleic acid. In otherembodiments, the present methods can further comprise contacting thesurface with a surfactant. Exemplary surfactants include an anionicsurfactant, a nonionic surfactant, a cationic surfactant as well as anamphoteric surfactant. In still other embodiments, the present methodscan further comprise contacting the surface with a solvent. Exemplarysolvents include an alcohol, an ester, a glycol ether, an amide, ahydrocarbon etc. In still other embodiments, the present methods canfurther comprise contacting the surface with an enzyme.

The present methods can be conducted at any suitable temperature range.In some embodiments, the present methods can be conducted at atemperature ranging from about 20° C. to about 40° C., e.g., about 20°C.-25° C., 25° C.-30° C., 30° C.-35° C., or 35° C.-40° C., or ambientconditions.

The present methods are preferably conducted at a near neutral pH of theperoxyformic acid compositions to avoid corrosion of the treatedsurfaces. In some embodiments, the pH is from about 4-9, 4.5-5.5, andpreferably 5.5-6.5. In a preferred aspect, the methods are conducted atnear neutral pH and thereby reduces and/or eliminates risk of corrosionto the surfaces being treated.

Beneficially, the methods of high level disinfection are suitable for insitu generation of the peroxyformic acid under conditions suitable forthe disinfection. In an aspect, the peroxyformic acid is generated andused within a matter of minutes at a point of use. In an aspect, atleast about 1 ppm peroxyformic is generated within less than 1 minute ofcontacting the first reagent and the second reagent. In an aspect, atleast about 1 ppm peroxyformic is generated within less than about 55seconds, 50 seconds or less, 45 seconds or less, 40 seconds or less, 35seconds or less, 30 seconds or less, 25 seconds or less, 20 seconds orless, 15 seconds or less, 10 seconds or less, or 5 seconds or less. Inan aspect, the reaction to form a liquid comprising at least about 1 ppmperoxyformic acid is near instantaneous. In an aspect, at least about100 ppm or at least about 500 ppm peroxyformic is generated within about5 minutes or less of contacting the first reagent and the secondreagent. In an aspect, at least about 100 ppm or 500 ppm peroxyformic isgenerated within less than about 4 minutes, 3 minutes or less, 2 minutesor less, or 1 minute or less.

In further aspects, the present peroxyformic acid forming compositionscan be configured to form a liquid, e.g., a solution, that comprises anysuitable concentration of peroxyformic acid within any suitable time.For example, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid and/or solid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 1 ppmperoxyformic acid within 1 minute of the contact time, e.g., at leastabout 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm or greaterof peroxyformic acid within 1 minute of the contact time.

In still further aspects, the solid composition can be configured to becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises at least about 1 ppm peroxyformic acid within 1minute of the contact time, e.g., at least about 1 ppm, 2 ppm, 3 ppm, 4ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm,30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm,75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm,3,000 ppm, 4,000 ppm, or 5,000 ppm or greater, of peroxyformic acidwithin 1 minute of the contact time.

Methods for Treating a Target or Surface Using a Saturated Wipe

In yet another aspect, the various methods for treatment using theperoxyformic acid generated according to the methods of the inventioncan be delivered using a saturated wipe. Disposable substrates arecommonly used in cleaning applications. Suitable substrates includewoven and nonwoven fabrics and various combinations thereof. Suchsubstrates can be impregnated with the peroxyformic acid generatedcompositions according to the invention or with the generatedperoxyformic acid at a point of use for application using the substrate.The resulting disinfecting products fabricated from such impregnatedsubstrates are accepted as a convenient and practical means for cleaningsurfaces, such as disclosed in U.S. Patent Publication No. 2014/0271762which is incorporated herein by reference in its entirety.

In an embodiment, microfiber products are used herein for the deliveryof the peroxyformic acid for consumer cleaning, such as thoseconstructed from split conjugated fibers of polyester and polyamide, oralternatively polyamide free versions. In an aspect, the peroxyformicacid generated according to the methods of the invention is used to coatthe substrate for contacting a surface. In another aspect, a first orsecond substrate for the peroxyformic acid generated according to themethods of the invention is impregnated into the substrate whichthereafter contacts the remaining chemistry (e.g. first or secondcomposition containing the other component for generating theperoxyformic acid) to generate the peroxyformic acid composition at apoint of use by a user.

The peroxyformic acid (or a first or second composition for generatingthe peroxyformic acid) coated onto the substrate may optionally furtherinclude one or more additives such as fragrances, dyes, pigments,emollients, bleaching agents, anti-static agents, anti-wrinkling agents,odor removal/odor capturing agents, ultraviolet light protection agents,insect repellency agents, souring agents, mildew removing agents,allergicide agents, and mixtures thereof.

In an embodiment, disinfectants are coated onto the substrate for lengthof times from about 20 seconds, 30 seconds, 45 seconds, 1 minute, 2minutes, 5 minutes, 10 minutes and up to about 7 days. Pre-coated wipesmay be sold in airtight containers. Such pre-coated wipes may be incontact with the disinfectant for seconds, to hours to days, andpreferably up to one week with the peroxyformic acid according to theinvention.

Methods for Skin and Surface Sanitizing and Disinfecting

In yet another aspect, the various methods for treatment using theperoxyformic acid generated according to the methods of the inventioncan be employed for skin sanitizing and disinfectant, including forexample methods for mastitis control. The rate of formation of theperoxyformic acid in situ is particularly beneficial for the applicationof use for skin disinfection. The disinfectant is generated in situ andprovides on demand disinfectant. Beneficially, the applications of useemploying the solid compositions for in situ generation of thedisinfectant peroxyformic acid provide glycerol as a leaving group whichis further beneficial to the skin treated with the disinfectantcomposition. Without being limited to a particular mechanism of actionand/or benefit, the glycerol provides an emmollient to the treated skinsurface. In an embodiment, the surface, including skin or other externalor mucosal surfaces of an animal in need of disinfectant is contactedwith an effective amount of peroxyformic acid for a sufficient time toreduce and/or remove microbial population on said treated surface.

The present methods can use any suitable concentration of peroxyformicacid for disinfecting skin by applying a liquid, namely a solution, tothe skin surface. In some embodiments, the present methods can comprisecontacting a surface with from about 10 ppm to about 1,000 ppmperoxyformic acid, e.g., 10-20 ppm, 20-30 ppm, 30-40 ppm, 40-50 ppm,50-60 ppm, 60-70 ppm, 70-80 ppm, 80-90 ppm, 90-100 ppm, 100-150 ppm,150-200 ppm, 200-250 ppm, 250-300 ppm, 300-350 ppm, 350-400 ppm, 400-450ppm, 450-500 ppm, 500-550 ppm, 550-600 ppm, 600-650 ppm, 650-700 ppm,700-750 ppm, 750-800 ppm, 800-850 ppm, 850-900 ppm, 900-950 ppm, or950-1,000 ppm peroxyformic acid. In a preferred aspect, the methods ofcontacting provide from about 10 ppm to about 500 ppm peroxyformic acidfor disinfectant generated in situ within a matter of minutes.

The present methods can comprise contacting a surface with an effectiveamount of peroxyformic acid for any suitable amount of time. In someembodiments, the present methods can comprise contacting a surface withan effective amount of peroxyformic acid for from about 1 minute toabout an hour, e.g., about 1 minute, 2 minutes, 3 minutes, 4 minutes, 5minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, or 10 minutes orgreater. In an aspect, the contacting time is preferably less than 10minutes, and more preferably less than 5 minutes. In an aspect, thecontacting occurs for a period of time before degradation of theperoxyformic acid composition.

The present methods can be used to treat a surface, including skin,having a contaminated surface from any suitable microbial populations.In some embodiments, the present method can be used to treat a surfacemade of or from a prokaryotic microbial population, e.g., a bacterial oran archaeal population. Exemplary bacterial populations include apopulation of Staphylococcus aureus, Streptococcus agalactiae,Streptococcus dysagalactiae, and Streptococcus uberis. The methods aresuitable for disinfecting common mastitis causing pathogens, includingboth contagious and environmental pathogens. Contagious bacteria, suchas Streptococcus agalactiae and Staphylococcus aureus, primarilycolonize host tissue sites such as mammary glands, teat canals, teatskin lesions etc. and are spread from one infected cow to another duringthe milking process. Environmental bacteria, often streptococci,enterococci and coliform organisms, are commonly present within thecow's surroundings from sources such as cow feces, soil, plant material,bedding or water, and infect by casual opportunistic contact with ananimal during the inter-milking period.

The methods of disinfecting a skin surface may include the contacting ofa surface with an effective amount of the disinfecting composition byvarious routes of application. In an aspect, the disinfectantcomposition can contact the surface by dipping the skin surface (such asteats) in solution, spray applying the solution to the surface, or bydipping in a foam produced from the solution. In a preferred aspect, amethod of treating teats of lactating animals comprises applying aneffective amount of the composition by dipping the teats in solution,spray applying the solution to teats, or by dipping in a foam producedfrom the solution.

The peroxyformic acid used in the present methods can be prepared usingany suitable methods disclosed herein. In some embodiments, theperoxyformic acid used in the present methods can be prepared bycontacting an ester of a polyhydric alcohol and formic acid, withhydrogen peroxide or a substance that generates hydrogen peroxide whenin contact with a liquid. For example, the peroxyformic acid used in thepresent methods can be prepared using any of the peroxyformic acidforming compositions described above or any of the methods describedabove. In other embodiments, the peroxyformic acid used in the presentmethods can be prepared in situ for the application of the formedperoxyformic acid.

In some embodiments, the present methods can further comprise contactingthe surface with a polyol, including a skin conditioning polyol, orother emollient and/or humectant. In an aspect, an emollient and/orhumectant is formulated with the disinfectant to lubricate, conditionand generally reduce and promote the healing of irritation on thesurface of application which may result either from the disinfectantagent, from mechanical action employed or from environmental conditionssuch as wind chill, dehydration, abrasion and sunburn. Any water solubleor dispersible skin conditioning agent may be used in this presentinvention. Compositions such as polyhydric alcohols are useful in theinvention including glycerin, sorbitol, mannitol, and propylene glycoland its homopolymers; fatty acid esters of simple monohydril alcoholsincluding isopropyl palmitate or isopropyl myristate and similar esters;polyol esters of fatty acids; and, ethoxylated lanolins, vegetable oils,and similar natural sourced derivatives such as aloe. Preferredemollients to be used in the invention include glycerin, sorbitol, andpropylene glycol.

In a preferred aspect, polyols include glycerin, propylene glycol,sorbitol, polyglycerol, and mixtures thereof. In a preferred aspect, thesurface is contacted with a disinfectant liquid, including a solutioncomprising the peroxyformic acid and the polyol in an amount from about0.5 wt-% to about 50 wt-% of the disinfectant liquid. In a preferredaspect, the surface is contacted with a disinfectant liquid, including asolution comprising the peroxyformic acid and the polyol in an amountfrom about 1 wt-% to about 10 wt-% of the disinfectant liquid.

In some embodiments, the present methods can further comprise contactingthe surface with the peroxyformic acid and a C₂-C₂₂ percarboxylic acid.Exemplary C₂-C₂₂ percarboxylic acids include peroxyacetic acid,peroxyoctanoic acid and/or peroxysulfonated oleic acid. In otherembodiments, the present methods can further comprise contacting thesurface with a surfactant. Exemplary surfactants include an anionicsurfactant, a nonionic surfactant, a cationic surfactant as well as anamphoteric surfactant. In still other embodiments, the present methodscan further comprise contacting the surface with a solvent. Exemplarysolvents include an alcohol, an ester, a glycol ether, an amide, ahydrocarbon etc. In still other embodiments, the present methods canfurther comprise contacting the surface with an enzyme.

In some embodiments, the present methods can further comprise contactingthe surface with the peroxyformic acid composition further comprisingsurface wetting agents. The surfactant or surfactant admixture of thepresent invention can be selected from compatible water soluble or waterdispersible nonionic, or anionic surface-active agents; or mixtures ofeach or both types. Nonionic and anionic surfactants offer diverse andcomprehensive commercial selection, low price; and, most important,excellent detersive effect—meaning surface wetting. Surface—active or“wetting agents” function to increase the penetrant activity of theinvention into the tissue surface at risk from mastitis causingpathogens. Nonionic surfactants useful in the invention are generallycharacterized by the presence of an organic hydrophobic group and anorganic hydrophilic group and are typically produced by the condensationof an organic aliphatic, alkyl aromatic or polyoxyalkylene hydrophobiccompound with a hydrophilic alkaline oxide moiety which in commonpractice is ethylene oxide or a polyhydration product thereof,polyethylene glycol. Practically any hydrophobic compound having ahydroxyl, carboxyl, amino, or amido group with a reactive hydrogen atomcan be condensed with ethylene oxide, or its polydration adducts, or itsmixtures with alkoxylenes such as propylene oxide to form a nonionicsurface-active agent. The length of the hydrophilic polyoxyalkylenemoiety which is condensed with any particular hydrophobic compound canbe readily adjusted to yield a water dispersible or water solublecompound having the desired degree of balance between hydrophilic andhydrophobic properties.

Also useful in the present invention are surface active substances whichare categorized as anionics because the charge on the hydrophobe isnegative; or surfactants in which the hydrophobic section of themolecule carries no charge unless the pH is elevated to neutrality orabove (e.g. carboxylic acids). Carboxylate, sulfonate, sulfate andphosphate are the polar (hydrophilic) solubilizing groups found inanionic surfactants. Of the cations (counterions) associated with thesepolar groups, sodium, lithium and potassium impart water solubility andare most preferred in compositions of the present invention. Examples ofsuitable synthetic, water soluble anionic compounds are the alkali metal(such as sodium, lithium and potassium) salts or the alkyl mononucleararomatic sulfonates such as the alkyl benzene sulfonates containing fromabout 5 to about 18 carbon atoms in the alkyl group in a straight orbranched chain, e.g., the salts of alkyl benzene sulfonates or of alkylnaphthalene sulfonate, dialkyl naphthalene sulfonate and alkoxylatedderivatives. Other anionic detergents are the olefin sulfonates,including long chain alkene sulfonates, long chain hydroxyalkanesulfonates or mixtures of alkenesulfonates and hydroxyalkanae-sulfonatesand alkylpoly (ethyleneoxy) ether sulfonates. Also included are thealkyl sulfates, alkyl poly (ethyleneoxy) ether sulfates and aromaticpoly (ethyleneoxy) sulfates such as the sulfates or condensationproducts of ethylene oxide and nonyl phenol (usually having 1 to 6oxyethylene groups per molecule).

In an aspect, oxidatively susceptible or acid hydrolytically susceptiblesurfactants are employed as wetting agents. Exemplary oxidativelysusceptible surfactants comprise polyethylene glycol based surfactant,polyglycerol, polyol sugar based surfactants, and mixtures thereof.Examplary surfactants include, alcohol ethoxylates, EO/PO copolymersexemplified by poloxamers, glycerol and polyglycerol ester surfactants,polysorbate surfactants exemplified by Tween® surfactants, and sugarbased surfactants exemplified by alkyl polyglucosides such as Glucopon®surfactants. Additional disclosure of suitable wetting agents is setforth in U.S. Pat. No. 6,749,869 and Reissue No. RE41279E, each of whichare herein incorporated by reference in their entirety. Beneficially,the disinfectant compositions are stable with peroxyformic acidcompositions generated in situ, unlike conventional food based or skinfriendly surfactants which are not stable in highly oxidative or verylow pH environments of traditional equilibrium or concentrate peracids.

In some embodiments, the present methods can further comprise contactingthe surface with the peroxyformic acid composition further comprising adye or colorant. In an aspect, the peroxyformic acid of the disinfectantcomposition is provided with a dye or colorant to provide a mechanismfor color marking of the disinfectant composition. Beneficially, theperoxyformic acid generated in situ does not have shelf-stability andformulation incompatibility with traditional colorants, as isexperienced with traditional equilibrium and concentrate peracidsystems. In an aspect, the dye or colorant is a food and/or drugadditive dye. In an aspect, the dye or colorant is not a color changingor indicator system. In an aspect, complexed iodines offer the advantageof being chromophoric, i.e. easily visible when applied onto the skin.Other antimicrobial agents do not have this feature; therefore,compositions of this invention may include a water soluble ordispersible coloring agent (dye or pigment or mixtures) which rendersthe composition chromophoric, having sharp contrast to teat skin andpermitting the dairy herd manager to visually discern that the teatshave been treated.

In further aspects, the disinfectant compositions may be comprised ofany number of optional ingredients. Generally, in accordance with theinvention, there may be included within this composition formularyadjuvants which assist in the application of the invention with respectto physical and chemical stability, barrier film formation, skin or teathealth maintenance, performance, physical form and manufacturing processanesthetics. Of course, these functions may be accomplished exclusivelyby composition ingredients already described or admixtures thereof;however, formulary or application or performance situations may occurrequiring additional effect which may be accomplished by introducing anadditional inorganic or organic agent or agents and mixtures thereofinto the composition.

The compositions of the invention may optionally include medicaments,for example sunscreens such as paraamino benzoic acid and healing agentssuch as allantoin or urea to provide curative action and stimulation offormation of new tissue; preservatives such as methyl paraben, propylparaben, sorbic and benzoic acids or salts thereof to retard bacterialgrowth and prolong shelf life; antioxidants such as BHT (butylatedhydroxytoluene), BHA (butylated hydroxyanisole), TBHQ(tert-butylhydroquinone), or propyl gallate to retard oxidative orhydrolytic degradation; sequestering agents such as aminopolyacetates,polyphosphonates, aminpolyphosphonates, polycarboxylates, and condensedphosphates; dispersants or suspending agents having polyelectrolyticcharacter such as polyacrylate and similar polycarboxylates ofhomopolymeric or copolymeric structure; and manufacturing processingagents, for example defoam additives employed to facilitate blending andmixing.

A wide variety of ingredients useful in skin disinfection, includingmastitis control, treatment can be included in the compositions hereof.This list is not intended to be exhaustive and other optionalingredients, which may not be listed, but which are well known in theart, may also be utilized in the composition. The examples are notintended to be limited in any way. In certain cases, some of theindividual adjuvants may overlap other categories. The adjuvantsemployed will be selected so as not to interfere with the antimicrobialaction of the composition and to avoid physical or chemical instabilityof the product.

The present methods can be conducted at any suitable temperature rangesas disclosed herein. In general, the pH of bovine mastitis controltreatments can vary from a low of about pH 2.0 to a maximum ofapproximately 11.0 depending primarily upon the choice of antimicrobialagent being incorporated in the composition because optimal efficacynormally occurs with a specific, narrow, pH range. Therefore thebuffering agent or system is chosen accordingly. The present methods arepreferably conducted at a slightly alkaline pH, or a near neutral pH ofthe peroxyformic acid compositions. In some embodiments, the pH is fromabout 2-9, 3-8, and preferably 4-7.

Beneficially, the methods of disinfection are suitable for in situgeneration of the peroxyformic acid under conditions suitable for thedisinfection. In an aspect, the peroxyformic acid is generated and usedwithin a matter of minutes at a point of use. In an aspect, at leastabout 1 ppm peroxyformic is generated within less than 1 minute ofcontacting the first reagent and the second reagent. In an aspect, atleast about 1 ppm peroxyformic is generated within less than about 55seconds, 50 seconds or less, 45 seconds or less, 40 seconds or less, 35seconds or less, 30 seconds or less, 25 seconds or less, 20 seconds orless, 15 seconds or less, 10 seconds or less, or 5 seconds or less. Inan aspect, the reaction to form a liquid comprising at least about 1 ppmperoxyformic acid is near instantaneous. In an aspect, at least about100 ppm or at least about 500 ppm peroxyformic is generated within about5 minutes or less of contacting the first reagent and the secondreagent. In an aspect, at least about 100 ppm or 500 ppm peroxyformic isgenerated within less than about 4 minutes, 3 minutes or less, 2 minutesor less, or 1 minute or less.

In further aspects, the present peroxyformic acid forming compositionscan be configured to form a liquid, e.g., a solution, that comprises anysuitable concentration of peroxyformic acid within any suitable time.For example, the first reagent and the second reagent in the presentperoxyformic acid forming compositions can be configured to be contactedwith each other to form a liquid and/or solid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the first reagent and the secondreagent can be configured to be contacted with each other to form aliquid, e.g., a solution, that comprises at least about 1 ppmperoxyformic acid within 1 minute of the contact time, e.g., at leastabout 1 ppm, 2 ppm, 3 ppm, 4 ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55ppm, 60 ppm, 65 ppm, 70 ppm, 75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900ppm, 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, or 5,000 ppm or greaterof peroxyformic acid within 1 minute of the contact time.

In still further aspects, the solid composition can be configured to becontacted with a liquid to form a liquid, e.g., a solution, thatcomprises any suitable concentration of peroxyformic acid within anysuitable time. In some embodiments, the solid composition can beconfigured to be contacted with a liquid to form a liquid, e.g., asolution, that comprises at least about 1 ppm peroxyformic acid within 1minute of the contact time, e.g., at least about 1 ppm, 2 ppm, 3 ppm, 4ppm, 5 ppm, 6 ppm, 7 ppm, 8 ppm, 9 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm,30 ppm, 35 ppm, 40 ppm, 45 ppm, 50 ppm, 55 ppm, 60 ppm, 65 ppm, 70 ppm,75 ppm, 80 ppm, 85 ppm, 90 ppm, 95 ppm, 100 ppm, 200 ppm, 300 ppm, 400ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1,000 ppm, 2,000 ppm,3,000 ppm, 4,000 ppm, or 5,000 ppm or greater, of peroxyformic acidwithin 1 minute of the contact time.

Methods for Treating Laundry Articles

In an aspect, the peroxyformic acid compositions are suitable fortreating laundry soils and cleaning articles, e.g., textiles, which havebecome soiled. In an aspect, additional functional ingredients,including those set forth in U.S. Publication No. 2013/0247308 (which isherein incorporated by reference in its entirety) can optionally be usedin combination with the peroxyformic acid compositions disclosed hereinfor laundry applications. The compositions of the present inventioneither in combination with additional functional ingredients, aloneand/or in combination with additional cleaning agents, can be used toremove stains from any conventional textile, including but not limitedto, cotton, poly-cotton blends, wool, and polyesters. The compositionscan be used on any item or article made from or including textilematerials, woven fabrics, non-woven fabrics, and knitted fabrics. Thetextile materials can include natural or synthetic fibers such as silkfibers, linen fibers, cotton fibers, polyester fibers, polyamide fiberssuch as nylon, acrylic fibers, acetate fibers, and blends thereofincluding cotton and polyester blends. The fibers can be treated oruntreated.

The laundry item can be processed in a laundry washing machine like awasher extractor or a tunnel washer. A washer extractor that can be usedincludes a drum having an interior for holding laundry, a motorconstructed and arranged for rotating the drum, a water inlet forintroducing water into the drum interior, a chemical inlet forintroducing chemicals into the drum interior, a drain for allowing fluidto drain from the drum interior, and a processing unit constructed foroperating the washer extractor. The processing unit can be constructedto provide a washing cycle for washing laundry with a cleaning anddisinfecting composition solution of the first component, a rinsingcycle for removing at least a portion of the detergent use solution, anda treatment cycle for treating laundry with a bleaching composition ofthe second component.

In conventional, industrial and/or commercial laundry washingapplications of use, the peroxyformic acid compositions can be employedfor removing soils from a textile either inside or outside a washingmachine, when employing a method of removing soils in a laundryapplication. In some aspects, when the composition is employed outsidethe washing machine it is used in a concentrated formulation. In otheraspects, when the composition is employed inside the washing machine itis used in a diluted (or a highly diluted) formulation, such as withinthe wash liquor of a washing machine in order to remove soils fromtextiles.

In a conventional, industrial laundry washing facility, textilematerials can be subjected to several treatment steps in an industrialsized laundry washing machine to provide cleaning. Exemplary treatmentsteps include a presoak or a prewash step, a wash step (e.g. soap andsuds step), a rinse step for the removal of soil containing wash liquor,a bleach step (separate or in combination with the wash step), severaloptional rinse steps to remove the bleaching composition, an optionalsour step to adjust the pH, softening step, and an extract step thatoften involves spinning the textiles to remove water. The compositionsof the invention can be employed in such exemplary conventional prewashor presoak steps, washing steps, and/or alternatively be used in washingtreatment steps that vary from such conventional processes. In addition,the compositions of the invention may be employed with a variety oflaundry washing machines, including industrial, commercial and/orconsumer machines (e.g. residential and/or home laundry washingmachine).

The method for treating laundry according to the invention can beprovided as part of an overall method for cleaning laundry according tothe invention. That is, as part of a laundry cleaning operation, thecompositions of the present invention can be used alone to treat thearticles, e.g., textiles, or can be used in conjunction withconventional detergents suitable for the articles to be treated. Alaundry cleaning process according to the invention can include theremoval of soil, the removal of staining or the appearance of staining,and/or the reduction of a population of microbes. The compositions ofthe invention can be used with conventional detergents in a variety ofways. Such formulation can include, for example, detergents for apre-wash or pre-soak step and/or a soap/suds/bleach step. In otherembodiments, the compositions of the invention can be used to treat thearticle as a separate additive from a conventional detergent. Thecompositions can be provided in the form of a concentrate that isdiluted with water to provide a use solution. Alternatively, thecompositions can be provided in the form of a use solution (alreadydiluted with water). When used as a separate additive, the compositionsof the present invention can contact the article to be treated at anytime. For example, the compounds and compositions of the invention cancontact the article before, after, or substantially simultaneously asthe articles are contacted with the selected detergent.

The use solution can be used for washing the articles. In an aspect, thecompositions can be applied to a prewash step (e.g. a warm about 40-50C). In certain aspects, low water levels are employed for the warmprewash step. Thereafter the removal of the excess grease and oily soilsfrom the surface of the article, the article can then be washedthoroughly in a main or conventional sud step (i.e. wash step) usingdetergents, bleaching agents and/or alkaline builders. In suchembodiments, the compositions contact the article before the articlesare contacted with the selected detergent, e.g. a pre-soak or a pre-washsituation, wherein the articles are contacted with the composition ofthe invention initially to emulsify soils on the substrate fabric. Thisstep may include a contact time from at least a few minutes. This stepmay optionally include the use of a builder or component compositionsfor providing a source of alkalinity, such as to increase the pH fromneutral to an alkaline pH, including for example of a pH of at least 10,or at least 11 or greater. The step may be conducted at a broad range oftemperatures.

In an embodiment, the compositions provides a suitable bleaching step,and may be combined with an additional bleaching and/or antimicrobialstep. This bleaching and antimicrobial step can follow or precede stepsof washing the laundry with a composition of the invention and drainingand/or rinsing the composition solution from the laundry. In otherapplications, it is expected that the bleaching and antimicrobial stepcan occur simultaneously with the washing step. It is expected that insituations where the soiling is relatively light, it may be advantageousto combine the washing step employing the emulsifying composition of theinvention with the bleaching and antimicrobial step. That is, thebleaching and antimicrobial step can include a soil removal step and/orit can occur before or after a soil removal step.

In an aspect of the invention, the composition is particularly suitedfor use as an additive composition within a regular wash/laundryprocess. For example, as disclosed herein the compositions can beemployed as a bleaching agent or booster to a regular suds bath (regularwash/laundry process) which already contains a main detergent,alkalinity, and/or possibly bleach. Such exemplary processes aredisclosed herein the description of the invention. Additionaldescription of suitable laundry methods which may employ thecompositions of the present invention are set forth, for example, inU.S. patent application Ser. No. 12/726,073, which is hereinincorporated by reference in their entirety.

In an aspect, the peroxyformic acid composition is employed at a pHvalue of a use solution, such as in the drum of a washer extractor or ina tunnel washer, at a pH from about 7 to about 14, from about 7 to about13, from about 7 to about 12, from about 7 to about 11, from about 7 toabout 10, from about 7 to about 9, or from about 7 to about 8.

EXAMPLES

The following examples are included for illustrative purposes only andare not intended to limit the scope of the invention.

Example 1 Perhydrolysis of Various Esters

Fifty (50) ppm various esters having the following structures

were added to 150 ppm H₂O₂ solution of pH 8.5 (DI water adjusted byadding 3.0 g of NaHCO₃ per liter of water and then adjusted pH withNa₂CO₃) respectively under ambient conditions. The concentration ofperoxycarboxylic acids were measured by an iodometric titration method.The results are summarized in Table 1 below and shown in FIG. 1.

TABLE 1 Perhydrolysis of various esters Peracid (ppm) Time (min)Glycerol formates Ethyl formate Triacetin 1 1.40 0.00 0.00 5 3.04 0.000.00 10 3.03 0.00 0.00 15 2.79 0.00 0.00 25 1.89 0.00 0.00 35 1.21 0.000.00

Beneficially as shown in Table 1 the glycerol formate ester providesrapid generation of peroxyformic acid. The initial measurement point forperacid generation was 1 minute, however, according to the invention theperacid generation is near instantaneous. As shown, only the glyercolformates generated performic acid under the tested conditions (i.e. lowpH), while no detectable peracid was generated using either ethylformate or triacetin under the same conditions.

The rate of generation of performic acid from the glycerol formate esteris distinct from that shown for the ethyl formate ester, such asdisclosed in U.S. Pat. Nos. 5,840,343 and 5,635,195 employing esters offormic acid (namely ethyl formate, methyl formate, and propyl formate)which fail to generate performic acid, nonetheless the rapid rate ofconversion into peroxyformic acid, as set forth in the claimed inventionand as evaluated according to this Example.

Example 2 Perhydrolysis of Various Polyhydric Alcohol Formic Acid Esters

Fifty (50) ppm various formic acid esters were added to 150 ppm H₂O₂solution of pH 8.5 (DI water adjusted by adding 3.0 g of NaHCO₃ perliter of water and then adjusted pH with Na₂CO₃) respectively underambient conditions. The concentration of peroxycarboxylic acids weremeasured by an iodometric titration method. The results are summarizedin Table 2 below and shown in FIG. 2.

TABLE 2 Perhydrolysis of 50 ppm various polyhydric alcohl formic acidesters in 150 ppm H₂O₂, pH 8.5 PFA (ppm) Glycerol PentaerythritolMannitol Time (min) formates formates formates 1 1.40 0.00 0.54 5 3.040.00 0.51 10 3.03 0.16 0.80 15 2.79 0.43 0.93 25 1.89 0.38 0.69 35 1.210.25 0.41

Example 3 Perhydrolysis of Glycerol Formates Under Various pH Conditions

Fifty (50) ppm glycerol formates was added to 150 ppm H₂O₂ solution ofvarious pHs (DI water adjusted by adding 3.0 g of NaHCO₃ per liter ofwater and then adjusted pH with Na₂CO₃) under ambient conditions. Theconcentration of peroxycarboxylic acids were measured by an iodometrictitration method. The results are summarized in Table 3 below and shownin FIG. 3.

TABLE 3 Perhydrolysis of glycerol formatted under various pH PFA (ppm)Time (min.) pH 8.0 pH 8.5 pH 9.0 1 0.32 0.99 2.90 5 0.96 2.20 3.58 101.56 2.78 3.53 15 1.94 2.53 2.64 25 1.77 1.40 1.17 35 0.96 0.77 0.68

Example 4 Generation of Peroxyformic Acid by Repeated Addition ofGlycerol Formates

Glycerol formates were added at various time point to 150 ppm H₂O₂solution of pH 8.0 (DI water adjusted by adding 3.0 g of NaHCO₃ perliter of water and then adjusted pH with Na₂CO₃) under ambientconditions. The concentrations of peroxycarboxylic acids generated weremeasured by an iodometric titration method. The results are summarizedTable 4 below and shown in FIG. 4.

TABLE 4 Generation of peroxyformic acid by repeated addition of glycerolformates to 150 ppm H₂O₂ solution, pH 8.0 50 ppm Glycerol 150 ppm H2O2Formate Volume pH 8.0 @ RT Time (min) Sample size (g) Thiosulfate (mL)[PFA] ppm 0.5 34.77 0.001 0.09 2.5 22.93 0.004 0.54 5 24.05 0.008 1.0310 32.9 0.016 1.51 15 27.85 0.016 1.78 20 28.03 0.014 1.55 25 21.820.008 1.14 30 24.22 0.006 0.77 35 26.83 0.006 0.69 TOTAL 243.4 1 HR Wait110 Add 38 uL Glycerol 0 0.00 Formate 110.5 28.53 0.002 0.22 113.5 28.550.008 0.87 115 22.12 0.008 1.12 120 23.52 0.014 1.85 125 23.29 0.0121.60 130 23.34 0.009 1.20 140 22.2 0.006 0.84 155 24.79 0.005 0.63 TOTAL439.74 1 HR Wait 255 Added 50 uL 0 0.00 Glycerol Formate = 89 ppm 255.522.05 0.004 0.56 257.5 28.12 0.02 2.20 260 24.8 0.024 3.00 265 26.580.03 3.50 270 26.15 0.03 3.56 275 24.52 0.028 3.54 285 26.32 0.026 3.06295 24.19 0.02 2.56 308 20.63 0.012 1.80 315 25.17 0.012 1.48 TOTAL688.27 16-18 HR Wait 1000 Added 15.6 uL of 0 0.00 Glycerol Formate = 89ppm 1000.5 21.68 0 0.00 1002.5 26.55 0.022 2.57 1005 25.93 0.026 3.111010 28.37 0.00 1015 15.86 0.018 3.52 1020 14.4 0.014 3.01 1025 20.290.018 2.75 1030 12.23 0.008 2.03 1040 15.52 0.007 1.40 1050 12.62 0.0040.98 TOTAL 881.72

Example 5 Perhydrolysis of Glycerol Formate in the Presence of Enzyme

Fifty (50) ppm of glycerol formates was added to 150 ppm H₂O₂ solutionof pH 8.0 (DI water adjusted by adding 3.0 g of NaHCO₃ per liter ofwater and then adjusted pH with Na₂CO₃) in the presence of various 10ppm (as product) enzyme under ambient conditions. The concentrations ofperoxycarboxylic acids generated were measured by an iodometrictitration method. The results are summarized in Table 5 below and shownin FIG. 5.

TABLE 5 Perhydrolysis of 50 ppm of glycerol formates in 150 ppm H₂O₂, pH8.0 in the presence of various enzymes PFA (ppm) Time Lipase Coronase48L Termanyl Esperease (min) Control (10 ppm) (10 ppm) (10 ppm) (10 ppm)0.5 0 0 0 0 0 2.5 0.32 0.64 0.48 0.32 0.31 5 0.96 0.97 1.13 0.63 1.23 101.56 1.60 1.92 1.27 1.61 15 1.94 1.29 1.93 1.40 2.22 20 1.77 0.96 2.021.26 2.18 30 1.40 0.80 1.93 1.39 1.92 40 0.96 0.64 2.02 1.30 1.85 500.85 1.83 1.22 1.66 60 1.18 1.61 75 1.09

Example 6 Suspension Test of PFA Generated Through Perhydrolysis fromGlycerol Formates in Cooling Tower Application

The antimicrobial efficacy of peroxyformic acid generated through theperhydrolysis of glycerol formatted were tested against pseudomonas incooling tower samples at both 25° C. and 37° C., along with theperoxyacetic acid (POAA) controls, and the results are summarized inTable 6 and 7 below.

TABLE 6 Microbial population (pseudomonas) in two cooling water samples(BP and Peninsula) 10 minutes after treatment with 5 ppm PFA from areaction between 200 ppm H₂O₂ and 170 ppm glycerol formate at 25° C.Exposure Test Avg. Log₁₀ Log₁₀ Water Condition Test Substance TimeTemperature Growth Reduction BP Cooling Water 5 ppm Ester PFA 10 minutes25° C. 2.74 2.93 pH 8.74 6.13 ppm POAA 4.10 1.57 12.3 ppm POAA 3.26 2.41Peninsula Cooling 5 ppm Ester PFA 2.76 2.42 Water pH 8.81 6.13 ppm POAA3.81 1.37 12.3 ppm POAA 3.30 1.88 Inoculum Numbers - BP Cooling Water +Conc. Water 5.67 Inoculum Numbers - Peninsula Cooling Water + Conc.Water 5.18

TABLE 7 Microbial population (pseudomonas) in two cooling water samples(BP and Peninsula) 10 minutes after treatment with 5 ppm PFA from areaction between 200 ppm H₂O₂ and 170 ppm glycerol formate at 37° C.Exposure Test Avg. Log₁₀ Log₁₀ Water Condition Test Substance TimeTemperature Growth Reduction BP Cooling Water 5 ppm Ester PFA 10 minutes37° C. 2.68 2.42 pH 8.74 6.13 ppm POAA 2.84 2.26 12.3 ppm POAA 2.73 2.37Peninsula Cooling 5 ppm Ester PFA 2.70 2.40 Water pH 8.81 6.13 ppm POAA2.76 2.34 12.3 ppm POAA 3.20 1.90 Inoculum Numbers - BP Cooling Water +Conc. Water 5.10 Inoculum Numbers - Peninsula Cooling Water + Conc.Water

Example 7 High Concentration Disinfection Test of Peroxyformic AcidGenerated Through Perhydrolysis Toward Various Microorganisms

The antimicrobial efficacy of PFA generated through the perhydrolysis ofglycerol formates were tested against various microorganisms in highconcentration disinfection test following the standard protocol, and theresults are summarized in Table 8 below.

TABLE 8 High Concentration Disinfectant Test of 270 ppm PFA Generatedthrough the Perhydrolysis of Glycerol Formates against VariousMicroorganisms Bacterial Disinfection Test Method: Use-dilution MethodExposure Test Substance Test System Time Results 13523-68-2 (~270 ppm S.aureus 1 minute 57/60 PFA, pH 2.18) P. aeruginosa 54/60 Clostridiumdifficile Disinfection Test Method: Modified 3 Step Method ExposureLog₁₀ Test Substance Test System Time Reduction 13523-68-1 (~270 ppm C.difficile 1 minute >5.72 PFA, pH 2.21)  3 minutes >5.72  5 minutes >5.7213523-68-1 (~270 ppm C. difficile 1 minute 6.04 PFA, pH 2.21) VirucidalActivity 13523-68-1 (~270 ppm Feline 1 minute >3.75 PFA, pH 2.21)Calicivirus (FCV) Polio virusType >4.50 1

Example 8 Preparation of Polyhydric Alcohol Formic Acid EstersPreparation of Glycerol Formates

To a 100 ml three neck flask equipped with a vacuum distillation head,was added 25 g (0.27 mol) of glycerin, followed by 54 g (1.17 mol) offormic acid. With magnetic stirring, the flask was slowly heated to 140°C. through an oil bath. The water generated from the reaction, alongwith some formic acid start to be distilled off when the temperature ofthe solution reached ˜115° C. As the reaction was completed (asevidenced by no distillate was come off), the distillation vacuum pumpwas turned on to remove the residual water and formic acid in thesolution, afforded 24 g of odorless, colorless liquid. NMR analysisindicates the product is a mixture of glycerol mono-, di- andtriformates.

Preparation of D-Mannitol Formates

Twenty (20) g of D-mannitol was dissolved in 60.65 g of 99% formic acidin a 100 ml of short-necked round-bottomed flask equipped a vacuumdistillation head and a magnetic stirrer. With stirring, the flask wasslowly heated to 120° C. by an oil bath. The water formed in thereaction and some excess amount of formic acid was distilled out slowly.When there was no distillate, the residual water and formic acid wasremoved by vacuum distillation. Afforded 25 g of odorless, colorlessviscous liquid. The liquid obtained slowly solidified to a white solidon storage under ambient conditions. The solid was further purified bywashing with ethyl acetate. The solid thus obtained has a melting pointof greater than 50° C., and is soluble in water. NMR analysis indicatesthe product is a mixture of mannitol mono-, di- and tri-, tetra-, penta-and hexaformates.

Preparation of Pentaerythritol Formates

Forty (40) g of pentaerythritol was dissolved in 108 g of 99% formicacid in a 250 ml of short-necked round-bottomed flask equipped a vacuumdistillation head and a magnetic stirrer. With stirring, the flask wasslowly heated to 120° C. by an oil bath. The water formed in thereaction and some excess amount of formic acid was distilled out slowly.When there is no distillate, the residual water and formic acid wasremoved by vacuum distillation. Afforded 39 g of odorless, colorlessviscous liquid. The liquid obtained slowly solidified to a white solidon storage under ambient conditions. The solid was further purified bywashing with ethyl acetate. The solid thus obtained has a melting pointof less than 50° C., and is soluble in water. NMR analysis indicates theproduct is a mixture of pentaerythritol mono-, di-, tri- andtetra-formates.

Preparation of Mannitol Hexaformates

Twenty (20) g of D-Mannitol was dissolved in 95 g of 99% formic acid ina 250 ml beaker. With stirring and cooling through an ice-water bath, 22g of phosphorus pentaoxide was slowly added to the solution. After theaddition of all phosphorus pentaoxide, large amount of precipitation wasformed. The mixture was prevented from the moisture and allowed to warmto room temperature and leave at ambient conditions overnight. Themixture was then added to 500 ml of cold water, and the solid wascollected by filtration, washed with 2% sodium bicarbonate solution,water, and dried at 50° C. Afforded 55 g of white solid. The solid ismarginally soluble in water at room temperature.

Example 9 Generation of PFA Through 850 ppm POAA+1% Glycerol Formatesand Imidazole

Eight hundred fifty (850) ppm POAA was made through the dilution of acommercially available peroxyacetic acid composition (5.6% POAA, 26%H₂O₂), referred to as POAA, using 5 grain tap water. One percent (1%)GlycForm with imidazole buffer was subsequently added to the POAAsolution. A 850 ppm POAA control was created by adjusting pH=5.00 withimidazole. The PFA generation kinetics as well as the pH profile of thesolution are shown in FIGS. 6A and 6B.

Example 10 Efficacy Against C. difficile Spores Using 850 ppm POAA Plus1.5% Glycerol Formates Versus 850 ppm POAA Control

To 850 ppm POAA prepared from a commercially available peroxyacetic acidcomposition (5.6% POAA, 26% H₂O₂), referred to as POAA, was added 1.5%glycerol formates with triazole buffer. Immediately after the mixing,the efficacy against C. difficile spores was tested following the EPA'sSOP “MB-31—Quantitative Disk Carrier Test Method (QCT-2) Modified forTesting Antimicrobial Products against Spores of Clostridium difficile(ATCC 43598) on Inanimate, Hard Non-porous Surfaces.” The contact timeis 3 minutes. As a comparison, 850 ppm POAA was tested under the sameconditions. The results are shown in FIG. 7. In addition, the efficacyagainst C. difficile spores were also tested 8 hours and 12 hours afterthe mixing of 850 ppm POAA and 1.5% glycerol formates with buffer, andthe results are shown in FIG. 8.

Example 11 Fast Generation of Performic Acid Through the Perhydrolysisof Glycerol Formates

Glycerol formates (0.5 g) was added to and mixed with 49.5 g of 1% H₂O₂solution at pH 9.0 buffered with the mixture of 0.1 M NaHCO₃ and 0.1MNa₂CO₃ (80 to 20 V:V). The PFA generated was monitored by an iodometrictitration method, and the pH of the solution was monitored by a pHmeter. The results are summarized in Table 9 and FIGS. 9A and 9B.

TABLE 9 Performic Acid Generation and the pH Profile Time (min) PFA(ppm) pH 0 0 9.0 0.25 673 8.14 1 709 7.56 3 598 7.17 5 447 7.00 10 3136.86 15 255 6.77 20 235 6.68 30 195 6.65

Example 12 General Procedure for the Preparation of Sugar Formates

To a round-bottom flask was added sugar and formic Acid (Table 10) withstir bar. The flask was placed in a 120° C., affixed to a distillationapparatus oil bath and allowed to stir until no more water or formicacid was distilled off (2-4 hours). The flask was then allowed to stirunder vacuum to strip off remaining liquid (1-2 hours). Product wascollected and the properties of the sugar formates are summarized in theTable 11.

TABLE 10 Amount of Sugars and Formic Acid Used for the Synthesis of theSugar Formates Sugar Alcohol Amount (g) Formic Acid Amount (g) Sucrose125.00 270.00 Dextrin (Maize) 15.63 33.75 Dextrin (Corn) 15.63 33.75Maltodextrin (4-7) 15.63 33.75 Maltodextrin (13-17) 15.63 33.75 SolubleStarch 15.63 33.75

TABLE 11 Physical Properties of Sugar Formates Prepared Water SugarFormates Form Color Hygroscopicity Soluble Sucrose Solid Dark BrownHighly Yes Dextrin (Maize) Solid Brown Medium Yes Dextrin (Corn) SolidLight Brown No Yes Maltodextrin (4-7) Solid Light Brown No YesMaltodextrin (13-17) Solid Light Brown Low Yes Starch Solid Light BrownMedium Yes

Example 13 Generation of Performic Acid from Sugar Formates throughPerhydrolysis

To 3% hydrogen peroxide solution of pH of 9.0 adjusted with 0.1MNaHCO₃/Na₂CO₃ was added 1% sugar formates, respectively. The performicacid formed was monitored by iodometric titration, and the pH wasmonitored by a pH meter, and the results are shown in FIGS. 10A and 10B.

Example 14 Reduction of P. aeruginosa Biofilm Using DifferentConcentrations of Peroxyformic Acid

P. aeruginosa ATCC 15442 biofilm was grown on the surface of 24polycarbonate coupons following ASTM method E2562-12: Standard TestMethod for Quantification of Pseudomonas aeruginosa Biofilm Grown withHigh Shear and Continuous Flow using CDC Biofilm Reactor. After 48 hoursof biofilm establishment, the coupons were removed from the reactor andplaced into individual centrifuge tubes. Three coupons per testsubstance were tested for disinfectant efficacy using ASTM methodE2871-12: Standard Test Method for Evaluating Disinfectant Efficacyagainst Pseudomonas aeruginosa Biofilm Grown in CDC Biofilm Reactorusing Single Tube Method. Each coupon was exposed to 4 mL of chemistryfor an exposure time of 3 hours. After which, 16 mL of neutralizingmedium was added on top of the chemistry to inactive antimicrobialperformance. This was followed with a series of vortexing and sonicatingsteps to remove any biofilm from the coupon surface into the solutionfor plating and enumeration. As shown in FIG. 11, peroxyformic acidachieves significantly greater anti-biofilm efficacy with aconcentration that is lower than POAA.

Example 15 Reduction of P. aeruginosa Biofilm Using Different ExposureTimes of Peroxyformic Acid

P. aeruginosa ATCC 15442 biofilm was grown on the surface of 24polycarbonate coupons following ASTM method E2562-12: Standard TestMethod for Quantification of Pseudomonas aeruginosa Biofilm Grown withHigh Shear and Continuous Flow using CDC Biofilm Reactor. After 48 hoursof biofilm establishment, the coupons were removed from the reactor andplaced into individual centrifuge tubes. Three coupons per testcondition were tested for disinfectant efficacy using ASTM methodE2871-12: Standard Test Method for Evaluating Disinfectant Efficacyagainst Pseudomonas aeruginosa Biofilm Grown in CDC Biofilm Reactorusing Single Tube Method. Sets of three coupons were exposed to 4 mL of50 ppm PFA for exposure times of 15 minutes, 30 minutes, 1 hour, 2 hoursand 3 hours, while coupons treated with 200 ppm POAA were exposed for 3hours only. After the desired exposure time, 16 mL of neutralizingmedium was added on top of the chemistry to inactive antimicrobialperformance. This was followed with a series of vortexing and sonicatingsteps to remove any biofilm from the coupon surface into the solutionfor plating and enumeration. As shown in FIG. 12, peroxyformic acidachieves greater anti-biofilm efficacy with shorter exposure time andlower concentrations than POAA.

Example 16 Stability of Glycerol Formates and Imidazole Premix

The accelerated stability of the premix of glycerol formates and pHadjustment reagent, i.e. imidazole was assessed by storing the premix in40° C. oven over 6 weeks, and the properties of the premix was evaluatedby the perhydrolysis with H₂O₂ under the same conditions. Thecomposition of the premix as well as the perhydrolysis conditions aresummarized in Table 12.

TABLE 12 Amount of Sugars and Formic Acid Used for the Synthesis of theSugar Formates Wt % Compositions Glycerol Formates (wt. %) Imidazole(wt. %) Premix 97 3 0.72 H₂O₂ 0.70 DI water 98.58 Total 100

The perhydrolysis kinetics of the glycerol premix stored for differentperiod of time is shown in FIG. 13 where under the accelerated storageconditions, there are effectively no differences among the glycerolformates premix stored up to 6 weeks.

Example 17 Generation of Performic Acid Through Perhydrolysis ofGlycerol Formates Premix

The generation of PFA from the perhydrolysis of glycerol formates andimidazole were evaluated under ambient conditions with variouscompositions, and the pH of the solution was also monitored as shown inTable 13 (GF—Glycerol formates; ID—imidazole).

TABLE 13 Perhydrolysis Compositions of Glycerol Formates PremixCompositions Composition A Composition B Composition C Composition D(wt. %) (wt. %) (wt. %) (wt. %) GF ID GF ID GF ID GF ID (wt. %) (wt. %)(wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) Premix 97.1 2.9 97.9 2.197.4 2.6 97.7 2.3 0.72 1.12 0.92 1.02 H₂O₂ 0.70 0.30 0.30 0.25 DI water98.58 98.58 98.78 98.73 Total 100 100 100 100

FIGS. 14-15 show PFA is generated very quickly under mild pH conditions,which make the resulting compositions particularly suitable fortreatment of surfaces or subjects requiring strong antimicrobialefficacy under more mild conditions, such as when non-corrosiveantimicrobial efficacy is desired, e.g. surgical instruments,endoscopes, etc.

Example 18 Reduction of E. coli Using Different Performic-Acid FormingCompositions

Nalidixic acid resistant E. coli O157:H7 was used to evaluate theefficacy in treatment with performic acid composition on raw beefbrisket according to the conditions shown in Table 14.

TABLE 14 Test Parameters Test System: Nalidixic acid resistant E. coliO157:H7 Test Substance Diluent: Sterile DI Water buffered to pH 9.5 withsodium bicarbonate and carbonate Red Meat: Beef flank steak/brisket, cutinto 5 cm square pieces Inoculation: 100 μl, spot inoculated and thenspread with a sterile hockey stick Attachment Time: 1 hour at 4° C.Treatment: Dip for 10 minutes, allowing chemistry to drain off of meatfor 15 seconds before neutralizing (3 samples a time) Neutralizer: 50 mLDE Broth Recovery: Stomached meat in neutralizer for 30 seconds at 230rpm Test Temperature Ambient Plating Medium: TSA with nalidixic acid (1ml/L media) Incubation: 35° C. for 48 hours Notes: Ester PFA turned meatwhite/gray during treatment

The generation of PFA from the perhydrolysis of glycerol formates, PFAformulations, POAA formations and controls were evaluated as shown inTable 15.

TABLE 15 Chemistry Preparations Test Use-solution Formula ConcentrationUse-solution Preparation pH A POAA 220 ppm POAA 0.79 g Commercial POAA/8.86 500 g Total B POAA + LAS 220 ppm POAA + 0.79 g Commercial POAA +8.88 50 ppm LAS 0.25 g 10% LAS/500 g Total C PFA 180 ppm PFA 0.95 gPFA/500 g Total 8.76 D PFA + LAS 180 ppm PFA + 0.95 g PFA + 0.25 g 10%8.79 50 ppm LAS LAS/500 g Total E Ester PFA (1% 180 ppm PFA 10 gGlycerol Formate + 10 g 6.61 H₂O₂, 2% Ester) 50% H₂O₂/500 g Total FEster PFA + LAS 180 ppm PFA + 10 g Glycerol Formate + 10 g 6.66 50 ppmLAS 50% H₂O₂ + 0.25 g 10% LAS/500 g Total G LAS  50 ppm LAS 0.25 g 10%LAS/500 g Total 9.47 H2O DI Water buffered to 9.51 pH 9.5 No TreatmentBackground

The micro results are shown in Tables 16-17, demonstrating improvedmicro efficacy (log reduction) achieved from PFA compositions incomparison to POAA.

Average Exposure Plate Plate Log Standard Log Log Test Substance TimeCount Dilution CFU/ml CFU/cm2 CFU/cm2 Deviation CFU/cm2 Reduction POAA10 minutes 60 10 6.00E+02 1.20E+03 3.08 0.09 2.98 1.06 220 ppm POAA, pH8.86 45 10 4.50E+02 9.00E+02 2.95 40 10 4.00E+02 8.00E+02 2.90 POAA +LAS 41 10 4.10E+02 8.20E+02 2.91 0.10 2.99 1.05 220 ppm POAA + 50 ppmLAS 63 10 6.30E+02 1.26E+03 3.10 pH 8.88 45 10 4.50E+02 9.00E+02 2.95PFA 92 10 9.20E+02 1.84E+03 3.26 0.06 3.22 0.83 180 ppm PFA, pH 8.76 7110 7.10E+02 1.42E+03 3.15 86 10 8.60E+02 1.72E+03 3.24 PFA + LAS 103 101.03E+03 2.06E+03 3.31 0.04 3.29 0.76 180 ppm PFA + 50 ppm LAS 87 108.70E+02 1.74E+03 3.24 pH 8.79 100 10 1.00E+03 2.00E+03 3.30 Ester PFA(1% H₂O₂, 2% 16 10 1.60E+02 3.20E+02 2.51 0.22 2.74 1.30 Ester) 31 103.10E+02 6.20E+02 2.79 180 ppm PFA, pH 6.61 43 10 4.30E+02 8.60E+02 2.93Ester PFA + LAS 26 10 2.60E+02 5.20E+02 2.72 0.26 2.71 1.33 180 ppmPFA + 50 ppm LAS 47 10 4.70E+02 9.40E+02 2.97 pH 6.66 14 10 1.40E+022.80E+02 2.45 LAS 41 100 4.10E+03 8.20E+03 3.91 0.15 3.78 0.27 50 ppmLAS, pH 9.47 31 100 3.10E+03 6.20E+03 3.79 21 100 2.10E+03 4.20E+03 3.62Water Control 27 100 2.70E+03 5.40E+03 3.73 0.06 3.80 DI H₂O Buffered topH 9.5 33 100 3.30E+03 6.60E+03 3.82 35 100 3.50E+03 7.00E+03 3.85Non-treated Controls 61 100 6.10E+03 1.22E+04 4.09 0.06 4.04 59 1005.90E+03 1.18E+04 4.07 47 100 4.70E+03 9.40E+03 3.97 Inoculum Numbers 42100000 4.20E+06 54 100000 5.40E+06 Background Numbers 25 10 2.50E+02 4610 4.60E+02

TABLE 17 Micro Efficacy Results Summarized Log Test Substance ReductionPOAA 1.06 220 ppm POAA, pH 8.86 POAA + LAS 1.05 220 ppm POAA + 50 ppmLAS pH 8.88 Ester PFA (1% H₂O₂, 2% Ester) 1.30 180 ppm PFA, pH 6.61Ester PFA + LAS 1.33 180 ppm PFA + 50 ppm LAS pH 6.66

As shown in the beneficially reduction of E. coli, the peroxyformic acidgenerated according to the methods of the invention provided an increasein micro efficacy over commercially available POAA and demonstratingsuitable application of use of the chemistry for contacting food tissueswith an alkaline PFA chemistry.

Example 19 Reduction of Aspergillus brasilensis (Anti-Fungal Activity)of Ester PFA

Aspergillus brasilensis ATCC 16403 was used to evaluate the efficacy intreatment with performic acid compositions according to the conditionsshown in Table 18.

TABLE 18 Test Parameters Test Systems: Aspergillus brasiliensis ATCC16403 Test Substances: Ester PFA - Target 440 ppm PFA Ester PFA - Target500 ppm PFA Test Substance Diluent: EN Synthetic Hard Water, pH 7.05Interfering Substance: Dirty Conditions Bovine Albumin Solution (3g/L) + sheep erythrocytes Exposure Time(s): 5 minutes and 10 minutesNeutralizer: 8 mL DE Broth + 1 mL sterile water Test Temperature: 20° C.Plating Medium: Oxoid MEA Incubation: 30° C. for 72 hours

The ester PFA compositions at varying ppm concentrations were evaluatedas shown in Table 19, with the micro results further shown in FIG. 16,demonstrating improved micro efficacy (log reduction) achieved from PFAcompositions in comparison to POAA.

TABLE 19 Micro Efficacy Results Test Exposure Log₁₀ Log₁₀ Test SubstanceTemperature Time Growth Reduction Ester PFA 20° C.  5 minutes 3.27 2.57320 ppm PFA 10 minutes 2.22 3.61 Ester PFA  5 minutes <2.15 >3.68 400ppm PFA 10 minutes <2.15 >3.68 Ester PFA  30 C.  5 minutes 2.19 3.64 320ppm PFA 10 minutes <2.15 >3.68 Ester PFA  5 minutes 1.48 4.36 400 ppmPFA 10 minutes <2.15 >3.68 Test Mixture Inoculum Numbers (N₀) 5.83Aspergillus brasiliensis ATCC 16404 6.83 Test Suspension Numbers (N)

Example 20 Fungicidal and Sporicidal Activity of Ester PFA

Various Bacillus and Aspergillus pathogens were used to evaluate themicro efficacy of ester PFA generated according to methods of thepresent invention. The test method, substance and results showing microefficacy of the PFA compositions are shown in Tables 20-23.

TABLE 20 Micro Efficacy Test Parameters and Results Test Expo- Log₁₀Temper- sure Log₁₀ Reduc- Test Substance ature Time Organic Soil Growthtion 350 ppm PFA 35° C. 5 minutes Dirty <2.18 >3.91 pH 5.88 Conditions300 ppm PFA (high <2.18 >3.91 pH 5.91 concentra- 250 ppm PFA tion bovine<2.18 >3.91 pH 5.82 albumin 200 ppm PFA solution + <2.18 >3.91 pH 5.81sheep eryth- rocytes) Test Mixture Inoculum Numbers (N₀) 6.09 Bacillussubtilis ATCC 6633 7.09 Test Suspension Numbers (N)

TABLE 21 Micro Efficacy Test Parameters and Results Test Expo- Log₁₀Temper- sure Log₁₀ Reduc- Test Substance ature Time Organic Soil Growthtion 350 ppm PFA 35° C. 5 minutes Dirty <2.18 >3.87 pH 5.88 Conditions300 ppm PFA (high <2.18 >3.87 pH 5.91 concentra- 250 ppm PFA tion bovine<2.18 >3.87 pH 5.82 albumin 200 ppm PFA solution + <2.18 >3.87 pH 5.81sheep eryth- rocytes) Test Mixture Inoculum Numbers (N₀) 6.05 Bacillussubtilis ATCC 19659 7.05 Test Suspension Numbers (N)

TABLE 22 Micro Efficacy Test Parameters and Results Test Expo- Log₁₀Temper- sure Log₁₀ Reduc- Test Substance ature Time Organic Soil Growthtion 350 ppm PFA 35° C. 5 minutes Dirty 3.46 2.65 pH 5.88 Conditions 300ppm PFA (high 3.38 2.73 pH 5.91 concentra- 250 ppm PFA tion bovine 3.552.56 pH 5.82 albumin 200 ppm PFA solution + >4.22 <1.89 pH 5.81 sheeperyth- rocytes) Test Mixture Inoculum Numbers (N₀) 6.11 Aspergillusbrasiliensis ATCC 16404 7.11 Test Suspension Numbers (N)

TABLE 23 Micro Efficacy Test Parameters and Results Test Expo- Log₁₀Temper- sure Log₁₀ Reduc- Test Substance ature Time Organic Soil Growthtion 350 ppm PFA 35° C. 5 minutes Dirty 2.23 3.91 Ester PFA pHConditions 300 ppm PFA (high 3.87 2.26 Ester PFA pH concentra- tionbovine albumin solution + sheep eryth- rocytes) Test Mixture InoculumNumbers (N₀) 6.14 Aspergillus brasiliensis ATCC 16404 7.14 TestSuspension Numbers (N)

Example 21 Sporicidal Activity of Ester PFA Versus POAA

Bacillus pathogens were used to evaluate the micro efficacy of ester PFAgenerated according to methods of the present invention in comparison toPOAA. The test methods are shown in Table 24 and the results are shownin Table 25 and FIG. 17.

TABLE 24 Test Parameters Test Systems: Bacillus subitilis ATCC 19659Test Substances: PFA (5.45% PFA) POAA (14.89% POAA) Test SubstanceDiluent: EN Synthetic Hard Water, pH 7.03 Test Substance Dilutions: 300ppm PFA pH 6.84 400 ppm PFA pH 7.19 368 ppm POAA (molar equivalent to300 ppm PFA) pH 6.73 490 ppm POAA (molar equivalent to 400 ppm PFA) pH6.78 Interferring Substance: Dirty Conditions Bovine Albumin Solution (3g/L) + sheep erythrocytes Exposure Time(s): 5 minutes, 10 minutesNeutralizer: 8 mL DE Broth + 1 mL sterile water Test Temperature: 20° C.Plating Medium: Oxoid TSA Incubation: 30° C. for 72 hours

TABLE 25 Results Log₁₀ Test Exposure Organic Average Log₁₀ Reduc-Substance Time Soil CFU/mL Growth tion 300 ppm PFA  5 minutes Dirty3.25E+03 3.51 2.28 pH 6.84 10 minutes Conditions 4.50E+01 1.65 4.14 400ppm PFA  5 minutes (high 3.45E+03 3.54 2.26 pH 7.19 10 minutesconcentra- 1.30E+03 3.11 2.68 368 ppm POAA  5 minutes tion bovine7.50E+05 5.88 0.00 pH 6.73 10 minutes albumin 5.00E+05 5.70 0.00 490 ppmPOAA  5 minutes solution + 8.50E+05 5.93 0.00 pH 6.78 10 minutes sheeperyth- 4.00E+05 5.60 0.19 rocytes) Test Mixture Inoculum Numbers (N/10)6.23E+05 5.79 Bacillus subtilis ATCC 19659 6.23E+06 6.79 Test SuspensionNumbers (N) Validation Test Suspension Numbers (N_(v)) 1.90E+02 ControlMixture Inoculum Numbers (N_(v0)) 1.90E+01 Control A Dirty 1.60E+01Conditions Control B 1.50E+01 Control C - PFA Dirty 1.70E+01 Control C -POAA Conditions 1.50E+01

As shown in FIG. 17 the PFA compositions generated according to themethods of the invention provide increased reduction in B. subtillisspores at both 5 and 10 minutes and at lower concentrations than POAAchemistries.

Example 22 Fungicidal/Yeasticidal Activity of Ester PFA Versus POAA

Canidia and Aspergillus pathogens were used to evaluate the microefficacy of ester PFA generated according to methods of the presentinvention in comparison to POAA. The test methods are shown in Table 26and the results are shown in Tables 27-28 and FIGS. 18-19.

TABLE 26 Test Parameters Test Systems: Candida albicans ATCC 10231Aspergillus brasiliensis ATCC 16404 Test Substances: PFA (9.48% PFA)POAA (14.95% POAA) Test Substance Diluent: EN Synthetic Hard Water, pH7.04 Test Substance Dilutions: 200 ppm PFA pH 6.15 300 ppm PFA pH 6.21245 ppm POAA (molar equivalent to 200 ppm PFA) pH 6.56 368 ppm POAA(molar equivalent to 300 ppm PFA) pH 6.63 Interferring Substance: DirtyConditions Bovine Albumin Solution (3 g/L) + sheep erythrocytes ExposureTime(s): 5 minutes, 10 minutes, 15 minutes Neutralizer: 8 mL DE Broth +1 mL sterile water Test Temperature: 20° C. Plating Medium: Oxoid MEAIncubation: 30° C. for 48 hours

TABLE 27 Results (Candida albicans) Log₁₀ Exposure Average Log₁₀ Reduc-Test Substance Time Organic Soil CFU/mL Growth tion 200 ppm PFA  5minutes Dirty <140 <2.15 >4.14 pH 6.15 10 minutes Conditions <140<2.15 >4.14 15 minutes (high <140 <2.15 >4.14 300 ppm PFA  5 minutesconcentra- <140 <2.15 >4.14 pH 6.21 10 minutes tion bovine <140<2.15 >4.14 245 ppm POAA  5 minutes albumin <140 <2.15 >4.14 pH 6.56 10minutes solution + <140 <2.15 >4.14 15 minutes sheep eryth- <140<2.15 >4.14 368 ppm POAA  5 minutes rocytes) <140 <2.15 >4.14 pH 6.63 10minutes <140 <2.15 >4.14 Test Mixture Inoculum Numbers (N₀) 1.94E+066.29 Candida albicans ATCC 10231 1.94E+07 7.29 Test Suspension Numbers(N) Validation Test Suspension Numbers (N_(v)) 5.55E+02 Control MixtureInoculum Numbers (N_(v0)) 5.55E+01 Control A Dirty 4.70E+01 ConditionsControl B 5.20E+01 Control C Dirty 4.80E+01 Conditions

TABLE 28 Results (Aspergillus brasiliensis) Log₁₀ Exposure Average Log₁₀Reduc- Test Substance Time Organic Soil CFU/mL Growth tion 200 ppm PFA 5 minutes Dirty 1.60E+04 4.20 1.54 pH 6.15 10 minutes Conditions1.75E+03 3.24 2.50 15 minutes (high 3.85E+02 2.59 3.16 300 ppm PFA  5minutes concentra- 4.10E+02 2.61 3.13 pH 6.21 10 minutes tion bovine1.20E+02 2.08 3.67 245 ppm POAA  5 minutes albumin >1.65E+05  >5.22<0.53 pH 6.56 10 minutes solution + >1.65E+05  >5.22 <0.53 15 minutessheep eryth- >1.65E+05  >5.22 <0.53 368 ppm POAA  5 minutesrocytes) >1.65E+05  >5.22 <0.53 pH 6.63 10 minutes >1.65E+05  >5.22<0.53 Test Mixture Inoculum Numbers (N₀) 5.59E+05 5.75 Aspergillusbrasiliensis ATCC 16404 5.59E+06 6.75 Test Suspension Numbers (N)Validation Test Suspension Numbers (N_(v)) 1.45E+02 Control MixtureInoculum Numbers (N_(v0)) 1.45E+01

As shown in FIG. 18 the PFA compositions generated according to themethods of the invention provide equivalent reduction in C. albicans at5, 10 and 15 minutes as POAA chemistries even when dosed at loweractives.

As shown in FIG. 19 the PFA compositions generated according to themethods of the invention provide improved reduction in A. brasiliensisconidio spores at 5, 10 and 15 minutes as POAA chemistries even whendosed at lower actives.

Example 23 Sporicidal Activity of Ester PFA Versus POAA

Additional Bacillus pathogens were used to evaluate the micro efficacyof ester PFA generated according to methods of the present invention incomparison to POAA. The test methods are shown in Table 29 and theresults are shown in Table 30.

TABLE 29 Test Parameters Test Systems: Bacillus subitilis ATCC 19659Test Substances: PFA (5.6% PFA) POAA (14.98% POAA) Test SubstanceDiluent: EN Synthetic Hard Water, pH 7.09 Test Substance Dilutions: 300ppm PFA pH 6.73 400 ppm PFA pH 6.95 368 ppm POAA (molar equivalent to300 ppm PFA) pH 6.88 490 ppm POAA (molar equivalent to 400 ppm PFA) pH6.65 Interferring Substance: Dirty Conditions Bovine Albumin Solution (3g/L) + sheep erythrocytes Exposure Time(s): 5 minutes, 10 minutesNeutralizer: 8 mL DE Broth + 1 mL sterile water Test Temperature: 20° C.Plating Medium: Oxoid TSA Incubation: 30° C. for 72 hours

TABLE 30 Results Log₁₀ Exposure Average Log₁₀ Reduc- Test Substance TimeOrganic Soil CFU/mL Growth tion 300 ppm PFA  5 minutesDirty >3.0E+05 >5.48 <2.26 pH 6.73 10 minutes Conditions 1.28E+05 5.112.63 400 ppm PFA  5 minutes (high >3.0E+05 >5.48 <2.26 pH 6.95 10minutes concentra- 7.50E+04 4.88 2.86 368 ppm POAA  5 minutes tionbovine >3.0E+06 >6.48 <1.26 pH 6.88 10 minutes albumin >3.0E+05 >5.48<2.26 490 ppm POAA  5 minutes solution + >3.0E+06 >6.48 <1.26 pH 6.65 10minutes sheep eryth- >3.0E+05 >5.48 <2.26 rocytes) Bacillus subtilisATCC 19659 5.45E+07 >7.74 Test Suspension Numbers (N) Validation TestSuspension Numbers (N_(v)) Control Mixture Inoculum Numbers (N_(v0))Control A Dirty Conditions Control B Control C Dirty Conditions

Example 24 Bactericidal Activity of Ester PFA Versus POAA

Additional Staphylococcus, Enterococcus and Pseudomonas pathogens wereused to evaluate the micro efficacy of ester PFA generated according tomethods of the present invention in comparison to POAA. The test methodsare shown in Table 31 and the results are shown in Tables 32-35 and FIG.20.

TABLE 31 Test Parameters Test Systems: Staphylococcus aureus ATCC 6538(0.217 A @ 620 nm) Enterococcus hirae ATCC 10541 (0.184 A @ 620 nm)Pseudomonas aeruginosa ATCC 15442 (0.191 A @ 620 nm) Test Substances:PFA (9.86% PFA) POAA (14.95% POAA) Test Substance Diluent: EN SyntheticHard Water, pH 7.04 Test Substance Dilutions: 20 ppm PFA pH 6.61 30 ppmPFA pH 6.74 50 ppm PFA pH 6.60 25 ppm POAA (molar equivalent to 20 ppmPFA) pH 6.73 38 ppm POAA (molar equivalent to 30 ppm PFA) pH 6.74 62 ppmPOAA (molar equivalent to 50 ppm PFA) pH 6.98 Interferring Substance:Dirty Conditions Bovine Albumin Solution (3 g/L) + sheep erythrocytesExposure Time(s): 5 minutes Neutralizer: 8 mL DE Broth + 1 mL sterilewater Test Temperature: 20° C. Plating Medium: Oxoid TSA Incubation: 35°C. for 48 hours

TABLE 32 Results Average Log₁₀ Log₁₀ Test Substance Exposure TimeOrganic Soil CFU/mL Growth Reduction 20 ppm PFA 5 minutes Dirty <140<2.15 >5.15 pH 6.61 Conditions 30 ppm PFA (High <140 <2.15 >5.15 pH 6.74concentration 50 ppm PFA Bovine <140 <2.15 >5.15 pH 6.60 Albumin 24.8ppm POAA Solution + 1.77E+05 5.25 2.05 pH 6.73 sheep 37.6 ppm POAAerythrocytes) <140 <2.15 >5.15 pH 6.90 62.4 ppm POAA <140 <2.15 >5.15 pH6.98 Test Mixture Inoculum Numbers (N_(o)) 1.97E+07 7.30 S. aureus ATCC6538 1.97E+08 Test Suspension Numbers (N) Validation Test SuspensionNumbers (N_(v)) 5.70E+02 Control Mixture Inoculum Numbers (N_(vo))5.70E+01 Control A Dirty Conditions 5.60E+01 Control B 7.40E+01 ControlC-A Dirty Conditions 5.90E+01 Control C-B 6.00E+01

TABLE 33 Results Average Log₁₀ Log₁₀ Test Substance Exposure TimeOrganic Soil CFU/mL Growth Reduction 20 ppm PFA 5 minutes Dirty 6.30E+033.80 3.46 pH 6.61 Conditions 30 ppm PFA (High 2.15E+02 2.33 4.92 pH 6.74concentration 50 ppm PFA Bovine <140 <2.15 >5.10 pH 6.60 Albumin 24.8ppm POAA Solution + >3.30E+05   >5.52 <1.74 pH 6.73 sheep 37.6 ppm POAAerythrocytes) 9.25E+03 3.97 3.29 pH 6.90 62.4 ppm POAA <140 <2.15 >5.10pH 6.98 Test Mixture Inoculum Numbers (N_(o)) 1.80E+07 7.26 E. hiraeATCC 10541 1.80E+08 Test Suspension Numbers Validation Test SuspensionNumbers (N_(v)) 4.30E+02 Control Mixture Inoculum Numbers (N_(vo))4.30E+01 Control A Dirty 7.70E+01 Conditions Control B 6.60E+01 ControlC-A Dirty 4.60E+01 Control C-B Conditions 5.30E+01

TABLE 34 Results Average Log₁₀ Log₁₀ Test Substance Exposure TimeOrganic Soil CFU/mL Growth Reduction 20 ppm PFA 5 minutes Dirty <140<2.15 >5.22 pH 6.61 Conditions 30 ppm PFA (High <140 <2.15 >5.22 pH 6.74concentration 50 ppm PFA Bovine <140 <2.15 >5.22 pH 6.60 Albumin 24.8ppm POAA Solution + <140 <2.15 >5.22 pH 6.73 sheep 37.6 ppm POAAerythrocytes) <140 <2.15 >5.22 pH 6.90 62.4 ppm POAA <140 <2.15 >5.22 pH6.98 Test Mixture Inoculum Numbers (N_(o)) 2.35E+07 7.37 P. aeruginosaATCC 15442 2.35E+08 Test Suspension Numbers Validation Test SuspensionNumbers (N_(v)) 5.05E+02 Control Mixture Inoculum Numbers (N_(vo))5.05E+01 Control A Dirty 8.40E+01 Conditions Control B 9.00E+01 ControlC-A Dirty 5.50E+01 Control C-B Conditions 4.30E+01

TABLE 35 Passing Requirements & Results Passing Requirements per EN1276: S. aureus E. hirae P. aeruginosa N is between 1.5 × 10⁸ CFU/mL N =1.97 × 10⁸ N = 1.80 × 10⁸ N = 2.35 × 10⁸ and 5.0 × 10⁸ CFU/mL N_(vo) isbetween 30 and 160 CFU/mL N_(vo) = 57 N_(vo) = 43 N_(vo) = 51 ControlsA, B, C are equal YES YES YES to or greater than 0.5 × N_(vo) A greaterthan 5 log₁₀ 20 ppm PFA-R = 20 ppm PFA-R = 20 ppm PFA- reduction (R) isachieved >5.15 3.46 R = >5.22 within the 5 minute contact 30 ppm PFA-R =30 ppm PFA-R = 30 ppm PFA- time: >5.15 4.92 R = >5.22 50 ppm PFA-R = 50ppm PFA-R = 50 ppm PFA- >5.15 >5.10 R = >5.22 25 ppm POAA-R = 25 ppmPOAA-R = 25 ppm POAA- 2.05 <1.74 R = >5.22 38 ppm POAA-R = 38 ppm POAA-R= 38 ppm POAA- >5.15 3.29 R = >5.22 62 ppm POAA-R = 62 ppm POAA-R = 62ppm POAA- >5.15 >5.10 R = >5.22

As shown in FIG. 20 the PFA compositions generated according to themethods of the invention provided at least substantially similar orimproved reduction in bactericidal activity against various pathogens,including medical pathogens and those related to skin disinfection.

Example 25 Summary of Fungicidal and Sporicidal Activity of Ester PFA

Various pathogens were used to evaluate the broad micro efficacyspectrum of ester PFA generated according to methods of the presentinvention. The test method, substance and results are shown in Table 36.

TABLE 36 Micro Efficacy Test Parameters and Results Test Passing MethodTest Substance Test Organisms Requirement Result EN 13727 450 ppm PFA P.aeruginosa 5 log reduction PASS pH 6-7 ATCC 15442 Staph. Aureus PASSATCC 6538 Enterococcus PASS hirae ATCC 10541 EN 13624 Canidia albicans 4log reduction PASS ATCC 10231 Aspergillus PASS brasiliensis ATCC 1604 EN13704 Bacillus subtilis 3 log reduction PASS ATCC 6633 EN 14476Poliovirus 4 log reduction PASS

Example 26 Hard Surface Testing with POAA and PFA from Ester Formate

Various pathogens were used to evaluate the broad micro efficacyspectrum of ester PFA generated according to methods of use for hardsurface disinfection. The test method, substance and results are shownin Table 37.

TABLE 37 Micro Efficacy Test Parameters and Results Test SubstanceExposure Time Test Results 850 ppm POAA + 1% Ester 3 minutes pH 4.44Test System Plate Count Culture Counts P. aeruginosa 27 31 S. aureus 6069 Average Average Test System Plate Count CFU/mL CFU/Carrier* NewCarrier P. aeruginosa 48 4.53E+05 4.53E+06 Counts 42 46 S. aureus 554.87E+05 4.87E+06 35 56

Example 27 Laundry Bleaching Efficacy of PFA

Laundry bleach testing to compare performance of performic acid andperacetic acid was performed with three different stains (coffee, curryand tea known to require bleaching actives for removal) on polyesterfibers at 40° C. for 10 minutes. A 15% peroxyacetic acid was compared at3 oz/cwt laundry dosing) to a peroxyformic acid on a equi-molar basis.In comparison, the performance of peracetic acid was also tested underthe same conditions with equal molar concentration. The result are shownin FIG. 21 comparing the percent of stain removal (bleaching efficacy)on the various stains. Beneficially, the peroxyformic acid is asefficient as peracetic acid as laundry bleach agent under the sameconditions.

Example 27 Laundry Disinfection Efficacy of PFA

The microbial efficacy of peroxyformic acid was also tested followingthe EPA protocol on 100% cotton carriers against a water control. Thetest conditions were pH 7.7, 500 ppm hard water, 40° C. and 5 minuteexposure time. In comparison, the performance of peracetic acid was alsotested under the same conditions. The results are summarized in Table38.

TABLE 38 Staphylococcus aureus ATCC 6538 Test Log Klebsiella pneumoniaemicroorganism survivors ATCC 4352 Test Conc. (CFU/ Log Log survivors Logsubstance (ppm) carrier) reduction (CFU/carrier) reduction Water 6.85n/a 6.12 n/a control Peracetic 42 <1.00 >5.85 3.66 2.46 acid Performic18 1.63 5.22 <1.00 >5.12 acid

As shown, despite peroxyformic acid being less than half of the dose ofperacetic acid, it delivers significant better kill than peracetic acid.

Example 28 Stability of PFA in Use Solution in the Presence of Soils

To 200 g of 500 ppm hard water containing individual soil load at thedesired concentration, was added PFA stock solution to target PFAconcentration of 500 ppm. The resulting solution was stored underambient conditions, and the level of PFA was monitored by iodometrictitration at the specific time point. The results are shown in FIG. 22demonstrating that despite the unstable nature of performic acid (shownby decrease in PFA concentration of the control), the soils tested hadno impact on the stability of PFA.

Example 29 Optimizing the Ratio of Glycerol Formate and an Acid PeroxidePremix for Performic Acid Generation

An ester of a polyhydric alcohol and formic acid (glycerol formate),hydrogen peroxide and an acid catalyst were combined without anyadditional water (outside of RM) added. Glycerol formate was preweighedinto a sample container. Acid premix (peroxide, sulfuric acid, anddeionized water) were preweighed into a second sample container. Thesecond sample container was poured into the first sample container andstarted timer followed by a brief period (<30 seconds of gentle mixing).At the time points noted in the data tables below, titrated mixture toquantitate performic acid and hydrogen peroxide content.

TABLE 39 Ratios evaluated Sample % by wt Glycerol Formate % by wt AcidPremix 1-1 64% 36% 1-2 60% 40% 1-3 56% 44% 1-4 45% 55% 1-5 35% 65%

TABLE 40 Acid Premix Composition Raw Material % by wt % active Peroxide(50%) 31.11 15.56 H2SO4 (50%) 66.67 33.34 DI Water 2.22 2.22

TABLE 41 Titration Results Time % Sample (min) PFA H202% 1-1 5 5.87%2.17% 1-1 10 5.83% 2.18% 1-1 20 5.80% 2.17% 1-1 122 5.67% 2.13% 1-2 56.10% 2.71% 1-2 10 6.21% 2.65% 1-2 20 6.15% 2.70% 1-2 60 6.08% 2.65% 1-35 6.16% 3.23% 1-3 10 6.33% 3.20% 1-3 20 6.43% 3.21% 1-4 1 2.57% 6.40%1-4 3 5.51% 5.11% 1-4 5 5.83% 4.89% 1-4 10 6.00% 5.12% 1-4 23 5.87%0.00% 1-5 3 5.57% 6.51% 1-5 5.5 6.16% 6.19% 1-5 10 6.12% 6.15% 1-5 206.14% 6.19% 1-5 90 5.91% 6.15%

Results are further shown in FIG. 23 depicting the peroxyformic acidgeneration using the glycerol formate and acid peroxide premix showinggenerated peak performic acid content achieved by 5 minutes. As depictedfrom about 5.5% to about 7% peroxyformic acid was generated in the 5minutes. The optimal ratio of the glycerol formate and acid peroxidepremix for maximizing peroxyformic acid yield is further depicted inFIG. 24.

Example 30 Optimizing the Composition of the Acid Peroxide Premix forPerformic Acid Generation

The methods of Example 29 were followed using the formulations shown inthe following tables to combine different ratios of an ester of apolyhydric alcohol and formic acid (glycerol formate), hydrogen peroxideand an acid catalyst.

TABLE 42 Ratios Evaluated Sample Sample Sample Sample Material 2-1 2-22-3 2-4 Glycerol Formate 64.00 64.00 64.00 64.00 Acid Peroxide Premix A36.00 0.00 0.00 0.00 Acid Peroxide Premix B 0.00 36.00 0.00 0.00 AcidPeroxide Premix C 0.00 0.00 36.00 0.00 Acid Peroxide Premix D 0.00 0.000.00 36.00

TABLE 43 Acid Premix Composition wt % of wt % of H202 H202 wt % of wt %of Material premix A premix B premix C premix D Peroxide (50%) 31.1162.00 31.11 62.00 H2SO4 (50%) 66.67 33.45 16.67 16.67 DI 2.22 4.55 52.2221.33

TABLE 44 Compositions (Active %) Sample 2-1 2-2 2-3 2-4 Glycerol 64.0064.00 64.00 64.00 Formate Peroxide 5.60 11.16 5.60 11.16 H2S04 12.006.02 3.00 3.00 DI 18.40 18.82 27.40 21.84

TABLE 45 Titration Results Time % Premix (min) PFA 2-2 1 1.25% 2-2 33.94% 2-2 5 7.14% 2-2 10 9.00% 2-2 30 9.68% 2-2 60 9.69% 2-2 120 9.50%2-2 180 9.41% 2-2 240 9.08% 2-2 5760 3.88% 2-2 10080 2.03% 2-3 1 0.23%2-3 4.5 0.41% 2-3 10 1.02% 2-3 40 3.64% 2-3 50 3.79% 2-3 60 3.73% 2-35760 1.61% 2-3 10080 0.87% 2-4 1 0.21% 2-4 3 0.94% 2-4 6 1.89% 2-4 83.37% 2-4 10.5 3.75% 2-4 15 5.40% 2-4 20 6.73% 2-4 30 7.89% 2-4 64 8.05%2-1 5 5.87% 2-1 10 5.83% 2-1 20 5.80% 2-1 122 5.67%

Results are further shown in FIG. 25 depicting the peroxyformic acidgeneration with the acid premix optimization, demonstrating sample 2-2provides the highest yield of peroxyformic acid within 10 minutes. Theresults of this Example yielded a higher percentage (about 10%)peroxyformic acid at a slower reaction than that of Example 29. Theresults illustrate the impact of the acid catalyst and pH of theformulations impact on the yield of peroxyformic acid.

The detailed description set-forth above is provided to aid thoseskilled in the art in practicing the present invention. However, theinvention described and claimed herein is not to be limited in scope bythe specific embodiments herein disclosed because these embodiments areintended as illustration of several aspects of the invention. Anyequivalent embodiments are intended to be within the scope of thisinvention. Indeed, various modifications of the invention in addition tothose shown and described herein will become apparent to those skilledin the art from the foregoing description which do not depart from thespirit or scope of the present inventive discovery. Such modificationsare also intended to fall within the scope of the appended claims.

All publications, patents, patent applications and other referencescited in this application are incorporated herein by reference in theirentirety for all purposes to the same extent as if each individualpublication, patent, patent application or other reference wasspecifically and individually indicated to be incorporated by referencein its entirety for all purposes. Citation of a reference herein shallnot be construed as an admission that such is prior art to the presentinvention.

The claimed invention is:
 1. A method for forming peroxyformic acidcomprising: contacting a polyhydric alcohol ester of formic acidcomprising glycerol formate with hydrogen peroxide to form a liquid thatcomprises peroxyformic acid, wherein the formed liquid comprises atleast 1 ppm peroxyformic acid within 1 minute, wherein the pH of saidformed liquid becomes 8 or lower within 1 minute after the contacting ofthe polyhydric alcohol ester of formic acid and hydrogen peroxidewithout the addition of an acidulant to decrease the pH of said formedliquid at any point after said contacting, and wherein the method forforming peroxyformic acid does not include an enzyme catalyst and/or asecond step of adding an acidulant to decrease the pH of said formedliquid.
 2. The method of claim 1, wherein the ester(s) further comprisespentaerythritol formates, mannitol formates, propylene glycol formates,sorbitol formates and sugar formates, and wherein the sugar formates aresucrose formates, dextrin formates, maltodextrin formates, or starchformates.
 3. The method of claim 1, wherein the polyhydric alcohol esterof formic acid and the hydrogen peroxide are contacted with each otherto form a solution that has a pH ranging from 6 to
 8. 4. The method ofclaim 1, wherein the polyhydric alcohol ester of formic acid and thehydrogen peroxide are contacted with each other to form a solution thathas a pH ranging from 4 to
 8. 5. The method of claim 1, wherein saidpolyhydric alcohol ester of formic acid and said hydrogen peroxide arekept separately prior to said contacting.
 6. The method of claim 1,wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted to form a solution that comprises at least 1 ppmperoxyformic acid within 30 seconds or less.
 7. The method of claim 1,wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted to form a solution that comprises at least 1 ppmperoxyformic acid within 15 seconds or less.
 8. The method of claim 1,wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted to form a solution that comprises at least 100ppm peroxyformic acid within 5 minutes or less.
 9. The method of claim1, wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted to form a solution that comprises at least 500ppm peroxyformic acid within 5 minutes or less.
 10. The method of claim1, wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted to form a solution that comprises peroxyformicacid under temperatures from 0° C. to 60° C.
 11. The method of claim 1,which further comprises using a stabilizing agent for peroxyformic acid,a stabilizing agent for hydrogen peroxide, and/or a pH buffering agent.12. The method of claim 11, wherein the stabilizing agent is phosphonatesalt(s) and/or a heterocyclic dicarboxylic acid.
 13. The method of claim1, wherein the formed liquid comprises from 1 ppm to 500,000 ppm of thepolyhydric alcohol ester of formic acid and 0.1 ppm to 100,000 ppm ofthe hydrogen peroxide.
 14. The method of claim 1, wherein the formedliquid comprises a solution that comprises from 0.1 ppm to 10,000 ppm ofperoxyformic acid.
 15. The method of claim 1, wherein the formed liquidcomprises a solution that comprises from 100 ppm to 1,000 ppm ofperoxyformic acid.
 16. The method of claim 1, wherein the polyhydricalcohol ester of formic acid and hydrogen peroxide are provided in asolid composition.
 17. The method of claim 16, wherein the solidcomposition comprises a stabilizing agent for peroxyformic acid, astabilizing agent for hydrogen peroxide and/or a pH buffering agent. 18.A method for forming peroxyformic acid comprising: contacting apolyhydric alcohol ester of formic acid comprising glycerol formates andhydrogen peroxide to form a liquid that comprises from 0.1 ppm to 10,000ppm of peroxyformic acid and wherein the pH of said formed liquidbecomes 8 or lower without the addition of an acidulant to decrease thepH of said formed liquid at any point after said contacting; wherein theester in the formed liquid comprises from 1 ppm to 500,000 ppm whereinthe hydrogen peroxide in the formed liquid comprises from 0.1 ppm to100,000 ppm, wherein the polyhydric alcohol ester of formic acid and thehydrogen peroxide are contacted to form a solution that comprises atleast 1 ppm peroxyformic acid within 1 minute of the contact time, andwherein the method for forming peroxyformic acid does not include anenzyme catalyst and/or a second step of adding an acidulant to decreasethe pH of said formed liquid.
 19. The method of claim 18, wherein thepolyhydric alcohol ester of formic acid and the hydrogen peroxide arekept separately prior to said contacting.
 20. The method of claim 18,wherein the polyhydric alcohol ester of formic acid and the hydrogenperoxide are contacted with each other to form a solution that has a pHranging from 5 to
 7. 21. The method of claim 18, wherein the polyhydricalcohol ester of formic acid and the hydrogen peroxide are contacted toform a solution that comprises at least 1 ppm peroxyformic acid within30 seconds or less.
 22. The method of claim 18, wherein the polyhydricalcohol ester of formic acid and the hydrogen peroxide are contacted toform a solution that comprises at least 1 ppm peroxyformic acid within15 seconds or less.
 23. The method of claim 18, wherein the polyhydricalcohol ester of formic acid and the hydrogen peroxide are contacted toform a solution that comprises at least 100 ppm peroxyformic acid within5 minutes or less.
 24. The method of claim 18, wherein the polyhydricalcohol ester of formic acid and the hydrogen peroxide are contacted toform a solution that comprises at least about 500 ppm peroxyformic acidwithin about 5 minutes or less.
 25. The method of claim 18, whichfurther comprises using a stabilizing agent for peroxyformic acid, astabilizing agent for hydrogen peroxide, and/or a pH buffering agent,and wherein the formed liquid comprises from 50 ppm to 40,000 ppm of theester of the polyhydric alcohol and formic acid, and from 150 ppm to50,000 ppm of the hydrogen peroxide.
 26. The method of claim 18, whereinthe polyhydric alcohol ester of formic acid and the hydrogen peroxideare contacted to form a solution that comprises from 1 ppm to 500 ppm ofperoxyformic acid.
 27. The method of claim 18, wherein the polyhydricalcohol ester of formic acid and hydrogen peroxide are provided in asolid composition.